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Getting Alolan Dugtrio
It can take quite a bit of time to find an Alolan Dugtrio in the game. A quicker method is to just catch a Diglett and evolve it into a Dugtrio. Diglett can be found on the first island. It can be found in the cave where you do your first trial. You first have to complete the trial before you can catch any Pokemon in that cave. You can also find Diglett in the cave next to the Pokemon Lab on the island. You need to be able to ride Taurus in order to break the rocks to enter it. After you catch Diglett, level it up. Diglett will evolve into Dugtrio at Level 26 -- so you need to use it quite a bit. You can also use some Rare Candies on it to level it up quicker. The "Exp All" does help level it up much quicker if you do not want to use it. If you do not want to level up Diglett, you will have to wait until the third island. You can catch it there and on the fourth island, but that is further into the game.
Munchlax and Snorlax Z
If you play the game during the launch window (until January 11, 2017), you can get Munchlax and Snorlax Z immediately. Start a new game and get your first Pokemon. Then, save and exit the game. At the main menu, select the "Mystery Gift" option, and choose the "Get Gift From Internet" selection to get Munchlax and the Snorlium Z for Snorlax. Munchlax can now be found at any Poke Center in the game. Talk to the guy next to the healing station, and he will tell you he has your gift. Munchlax will be Level 5 and can be either male or female. To evolve Munchlax, you need to max its affection with you. You can do this by feeding it, using it in battle, petting it in the groom section, and cleaning dirt or other things off it after battle. When you max the affection, it will evolve the next time it levels up. When you get Snorlax, give it the Snorlax Z stone to give it a special ability.
Successfully complete the main quest and defeat all four Island Kahunas to become the Alola Champion. Go back to the Altar Of The Moon. Enter the Portal at the Altar, then go to the Lake Of The Sun. Go to the platform at the top of the lake to initiate a cutscene. Cosmog will join your party. Note: You can only get one Cosmog per playthrough.
You cannot catch Eevee until you reach the second island. You will get a mission early while on the second island to go to a Pokemon Ranch. On the way to the Pokemon Ranch, you can find Eevee spawns right before the town, near the ranch. However, it is rare for them to spawn. You can also find them on the other side of the map, on Route 5 coming down from the ranch. Eevee will often call for extra help -- so be prepared for that. You can evolve Eevee into multiple different forms.
Get Cosmog, then evolve it. Cosmog will evolve into Cosmoem, and Cosmoem will evolve into Lunala. Lunala is a Psychic/Ghost type.
Go to Hau'oli City after your first trial when Pokemon can call for help. Enter the fenced area across from the mall. Walk around in that grass until you run into a Pichu. Note: Set another Pichu or Pikachu with Static as the first member of your party to increase the odds of a Pichu appearing. This is best done in the area on Route 1 where Pichu spawns, as this does not also have a Magnemite. Stall the battle until Pichu calls for help. Get the Pichu to low HP to increase rate of it calling for help. The Pokemon it calls for help will either be Pikachu, Pichu, or Happiny. It calls Pikachu 4/7 of the time, another Pichu 2/7 of the time, and Happiny 1/7 of the time. If it is Pikachu, K.O. the Pichu and catch the Pikachu. If it is Pichu or Happiny, K.O. the new Pichu or Happiny and stall the battle again until Pichu calls for help and it is Pikachu.
There are seven exclusive Pokemon each in Pokemon Sun and Pokemon Moon. The following is a list and description of all 14 exclusive Pokemon:
Lycanroc (Midday Form; Rock type): The second form and first evolution of Rockruff is a wolf-like Pokemon that lives alone. While still threatening, the Midday Form of Lycanroc isn't nearly as menacing as the werewolf-like menace exuding from her brother, the Lycanroc Midnight Form. In its midday form, it retains the light-brown colors and looks much more like a wolf, ready to pounce on prey.
Ninetails (Alolan Form; Ice/Fairy type): The Alolan evolution for Vulpix, Alolan Ninetails becomes a dual-type with the addition of Fairy. This chilly Ninetails features a billowing tail, making it resemble a freezing winter fog. It has adapted to live on high peaks and traverse freezing conditions on mountains.
Passimian (Fighting type): A Pokemon that's all about teamwork, Passimian works together with a pack, passing hard-shelled berries to help friends or hurt enemies. Seen taking a Quarterback-like stance, Passimian even wears a green helmet fashioned from hard Alolan berries.
Solgaleo (Psychic/Steel type): The sol-based Legendary found only in Pokemon Sun comes in two phases — normal, and Radiant Sun. When transformed, Solgaleo can expend the vast amounts of solar energy from its body, and glows brightly. This Pokemon can't be captured by normal means. Only the strongest trainers will be able to calm it's burning personality.
Turtonator (Fire/Dragon type): This explosive turtle Pokemon features elements of a common tortoise mixed with a landmine. That makes a tough combination, and the fire type / dragon type combo only makes sense for a fire-breather. The heavy shell it uses to protect itself makes this tank-like Pokemon ideal for the lava-filled volcano environments found in Alola.
UB-02 Absorption: This Ultra Beast only appears in Pokemon Sun, and resembles a massive, muscular lobster. This massive creature is all about physical attacks and high defense, and can bring the pain with its over-sized fists, raining punches on unsuspecting Pokemon and their trainers if they're not ready for a tough fight.
Vulpix (Alolan Form; Ice type): Vulpix and Ninetails return in Pokemon Sun with their all-new Alolan forms. Switched from their traditional fire type, both are now ice type due to their living conditions on a cold Alolan island. Although it doesn't visit warm climates often, Alolan Vulpix can lower the temperature of an area on command.
Drampa (Normal/Dragon type): Another dual-type, this calming sea monster comes from the skies high above the Alola region. Looking something like a Chinese Dragon (think Dragon Ball Z), this chill creature rides on a wave. It likes to move slow, take its time, and doesn't really like going up stairs. Constantly riding on a cloud, Drampa loves nothing more than caring for its children.
Lunala (Psychic/Ghost type): The Legendary of Pokemon Moon is a massive bat with guillotine-like wings. It is the opposite of Pokemon Sun's Solgaleo, and absorbs dark energy into its body instead of light. The Full Moon form changes the colors of Lunala so it more closely resembles a complete moon, right before unleashing its deadly psychic abilities.
Lycanroc (Midnight Form; Rock type): The aggressive, and red-hued Midnight Form of Lycanroc loves to fight, and it shows. Looking more like a werewolf than a regular wolf, Midnight Form Lycanroc walks on two feet, and remains permanently hunched over, coiled and ready to attack.
Oranguru (Normal/Psychic type): This wise old orangutan lives alone, deep in the forests, where it can calmly ponder the mysteries of life. Orangurus, according to legend, were once mistaken for humans deep in the Alolan forests, due to their highly intelligent nature.
Sandshrew (Alolan Form; Ice/Steel type): Leaving the ground, the chilly Sandshrew has adapted to Alola and become a dual-type; Ice and Steel. Like the ice Vulpix, Sandshrew also migrated to the freezing mountains of the Alolan region where it took on new traits.
Sandslash (Alolan Form; Ice/Steel type): Replacing quills with even bigger icicles, the Alolan Sandslash uses its claws to carve through the snow on high mountains where most trainers won't dare tread. They might be rare, but photographers covet Sandslash sightings due to the snow they kick up.
UB-02 Beauty: The exclusive Ultra Beast found in Pokemon Moon is UB-02 Beauty, a slender mantis-like being that can move faster than lightning. Its strange features sap the will to fight from trainers, suggesting it will lean more heavily on buffs / debuffs when you encounter it later in the story.