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Excluding the rival and battle facilities. Also specify which one(s) they use.

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Do you mean All pokemon Role-Playing games, or literally all pokemon games?
I know in RSE there are none. In Pt, Gardenia uses Turtwig, Ace Trainer Alyssa uses Grotle, Ace Trainer Sydney uses Torterra, Camper Anthony uses Chimchar, Pokemon Ranger Jeffery uses Monferno, Flint uses Infernape, Picnicker Karina uses Piplup, Rich Boy Jason uses Prinplup, and Veteran Edgar uses Empoleon.
Sorry I meant the Role-Playing games
Professor Sycamore in XY uses tthe Gen 1 starters all of them. he battles you a few times
FRLG has just random NPCs that use each the Kanto starters and their evolutions at least once; by the time you've reached the E4, you should have seen all 9 of them, regardless of which one you picked. I'm not sure where each of these NPCs are, though. I just remember that from my playthrough.
I think in Generation 7, Kukui and a few people at the Trainer's School use starters.
I'm sure that I read somewhere that Venusaur was unregisterable as seen in Kanto if Charmander was picked though.
https://pokemondb.net/pokebase/260397/trainers-with-wartortle-blastoise-in-r-b?show=260400#a260400 Here's an answer for Red/Blue. I might work on an answer for the other games.

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Note that I will not be specifying which evolution of starter that each trainer listed uses. It would take a bit more time, and answering this is already going to take a lot of time, so, instead, I'm just going to tell which starter evolution line the trainer has. If you would like to know which starters each listed trainer specifically has, either check my source or ask in a comment on this answer.

Red/Blue/Yellow:

A list of trainers with starter Pokemon in Red/Blue/Yellow can be found here

Gold/Silver/Crystal:

Bulbasaur/Ivysaur/Venusaur:
Cooltrainer♂ Aaron
Cooltrainer♀ Megan
Cooltrainer♂ Nick
Picnicker Gina
Lass Linda
Pokéfan♂ Carter
Red

Charmaner/Charmeleon/Charizard:
Cooltrainer♂ Aaron
Cooltrainer♂ Allen
Cooltrainer♂ Kevin
Cooltrainer♂ Nick
Firebreather Dick (Gold/Silver)
Pokéfan♂ Carter
Red

Squirtle/Wartortle/Blastoise:
Cooltrainer♂ Aaron
Cooltrainer♀ Joyce
Cooltrainer♂ Kevin
Cooltrainer♂ Nick
Pokéfan♂ Carter
Red

FireRed/LeafGreen:

Bulbasaur/Ivysaur/Venusaur:
Beauty Olivia
Cooltrainer♂ Albert
Cooltrainer♀ Mary
Cooltrainer♂ Rolando
Picnicker Martha
Picnicker Tina
Aroma Lady Violet
Blue (If player chose Squirtle)

Charmaner/Charmeleon/Charizard:
Burglar Arnie
Cooltrainer♂ Rolando
Camper Chris
PokéManiac Dawson
PokéManiac Steve
Twins Kiri & Jan
Blue (If player chose Bulbasaur)

Squirtle/Wartortle/Blastoise:
Cooltrainer♂ Colby
Cooltrainer♂ Rolando
Camper Ricky
Swimmer♂ Garrett
Swimmer♂ Jerome
Swimmer♂ Mymo
Twins Kiri & Jan
Blue (If player chose Charmander)

Diamond/Pearl:

Turtwig/Grotle/Torterra:
Ace Trainer♀ Alyssa
Ace Trainer♀ Sydney
Aroma Lady Angela
Gardenia
Ace Trainer Sydney

Chimchar/Monferno/Infernape:
Ace Trainer♂ Dennis
Flint

Piplup/Prinplup/Empoleon:
Picnicker Karina
Pokémon Ranger♂ Jeffery
Veteran Edger

Platinum:

Turtwig/Grotle/Torterra:
Ace Trainer♀ Alyssa
Gardenia
Ace Trainer Sydney

Chimchar/Monferno/Infernape:
Black Belt Eddie
Flint
Camper Anthony
Pokémon Ranger♂ Jeffery

Piplup/Prinplup/Empoleon:
Picnicker Karina
Pokémon Ranger♂ Kyler
Rich Boy Jason
Veteran Edgar

HeartGold/SoulSilver:

Bulbasaur/Ivysaur/Venusaur:
Ace Trainer♂ Alton
Ace Trainer♀ Megan
Ace Trainer♂ Nick
Ace Trainer♀ Quinn
Picnicker Gina
Lass Linda
Pokéfan♂ Carter
Red

Charmander/Charmeleon/Charizard:
Ace Trainer♂ Allen
Ace Trainer♂ Alton
Ace Trainer♂ Kevin
Ace Trainer♂ Nick
Firebreather Richard
Pokéfan♂ Carter
Red
Clair

Squirtle/Wartortle/Blastoise:
Ace Trainer♂ Alton
Ace Trainer♀ Joyce
Ace Trainer♀ Kelly
Ace Trainer♂ Kevin
Ace Trainer♂ Nick
Swimmer♂ Randall
Pokéfan♂ Carter
Red

Chikorita/Bayleef/Maganium:
Ace Trainer♂ Cal

Cyndaquil/Quilava/Typhlosion:
Ace Trainer♂ Cal

Totodile/Croconaw/Feraligatr:
Ace Trainer♂ Cal

X/Y:

Bulbasaur/Ivysaur/Venusaur:
Professor Sycamore

Charmander/Charmeleon/Charizard:
Professor Sycamore

Squirtle/Wartortle/Blastoise:
Professor Sycamore

Sun/Moon:

Bulbasaur/Ivysaur/Venusaur:
Red

Charmander/Charmeleon/Charizard:
Red

Squirtle/Wartortle/Blastoise:
Red

Rowlet/Dartrix/Decidueye:
Professor Kukui (If player chose Popplio)

Litten/Torracat/Incineroar:
Professor Kukui (If player chose Rowlet)

Popplio/Brionne/Primarina:
Professor Kukui (If player chose Litten)

Ultra Sun/Ultra Moon:

Rowlet/Dartrix/Decidueye:
Teacher Emily (If player chose Popplio)
Professor Kukui (If player chose Popplio)

Litten/Torracat/Incineroar:
Teacher Emily (If the player chose Rowlet)
Professor Kukui (If player chose Rowlet)

Popplio/Brionne/Primarina:
Teacher Emily (If the player chose Litten)
Professor Kukui (If player chose Litten)

Source

I'm pretty sure that I got all of them, but there is a chance that I missed at least one. If anyone does notice that I missed any, please comment below and tell me what I've missed! I'll edit it in as soon as I can.

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You forgot Gardenia, Ace Trainer Sydney, and Veteran Edgar.
Yeah, I've probably forgotten a lot. I've only looked through the trainer classes for the first three generations on the Bulbapedia page, so I've still got quite a bit more to go.
Doesnt pkmn trainer cedric use turtwig in route 203 on sinnoh?
There isn't even a Pokemon trainer named Cedric on Route 203.
It would be barry
Read the question. It said to exclude rivals.