PokéBase - Pokémon Q&A
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This is something I've been wondering for a while. Outside of Wally's wild Ralts and Professor Juniper's Minccino, can enemy or NPC trainers in any other game have a chance to have a Shiny Pokemon?

(There are various Trainer Tower battles in Fire Red/Leaf Green that have Shiny Pokemon, but these are always forced to be Shiny and not a random chance.)

Ouch, hadn't seen that, sorry.

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Only in the Battle Frontier / Subway / Tree / etc., where they have the same probability as random shinies. Other than that, there is one trainer in the main series games with a guaranteed shiny: a sightseer (Markus) in Seafolk Village in SM/USUM (credit to Dragonblade). After searching on Bulbapedia I couldn’t find any other examples of trainers with shinies, which would be predetermined for any trainer outside of the battle facilities.

edited by
There is the trainer with a shiny exeggcute in SM
Apparently I also forgot to note that enemy trainer's Shadow Pokemon in Colosseum can be Shiny and Shadow, but the shininess is weird in that it might be shiny for the enemy but not for the player, or it might BECOME shiny when the player snags it