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Please don't question my curiosity.

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Outside of the Battle Royale and Battle Tree, there are no NPCs that use Megas.
I honestly forgot who uses Megas in the Royale and Tree. :l
Dexio uses a Mega Stone

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Battle Tree

  • Red, Blue, Anabel, Colress, Cynthia, Sina, Dexio, Grimsley, Guzma, Kiawe, Mallow, Plumeria, Wally
  • Aino, Alim, Anisa, Arnold, Arnon, Atalanta
  • Benji, Bette, Boris, Brantly, Bryson, Buddy
  • Cadel, Cal, Calder, Calliope, Camber, Candy, Carrie, Chip, Christian, Christy, Chucky, Colby
  • Dan, Danby, Dara, Darrel, Dennis, Dolly, Donna, Donny, Dooley, Dustin, Dyson
  • Edda, Erix, Etta, Ezra
  • Fernanda
  • Gertrude, Gilroy, Gracie, Granville
  • Haley, Harding, Harvey, Hashim, Heidi, Hilario
  • Ignacio, Iniko, Izel
  • Jairo, Jana, Jo, Joaquin, Julien
  • Kiernan, Kikujiro
  • Larry, Lea, Leena, Levi, Lori, Luke
  • Marianne, Munin
  • Naya, Nedry, Niara, Noah
  • Omar
  • Patrick, Paulo, Perri, Poppy, Presta
  • Rada, Raz, Reina, Rendor, Robyn
  • Sam, Samantha, Savir, Sheridan, Sika, Sly, Stein, Stellan, Sylvia
  • Tamah, Tasanee, Thamina, Tivon, Tony
  • Variel, Verna, Victor, Vivek
  • Xenophon, Xio
  • Zed, Zero

Battle Royal

I'm just going to give a link for this one now and add the list later because this is exhausting.

Other

  • Dexio
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Are you sure that's the complete list? I remember that Mallow uses a mega Sceptile at some point.
she does, but Mallow is already on the list
Yeah, she's right up in the first line.
Also do you want me to complete it or should I leave it as-is with just the link.
I see it now. You can do whatever you want as long as the answer is complete and readable.
By the way, will you include Battle Royal information in this answer?
I will as soon as I have time to add it.