All Pokémon that can learn TMs can learn Substitute. -Bulbepedia
These Pokemon can't learn any TMs:
Caterpie
Metapod
Weedle
Kakuna
Magikarp
Ditto
Unown
Wobbuffet
Smeargle
Wurmple
Silcoon
Cascoon
Wynaut
Beldum
Kricketot
Burmy
Combee
Tynamo
Source^
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