PokéBase - Pokémon Q&A
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It is in Twist Mountain. Unfortunatly, many items in Twist Mountain can only be obtained in Winter, including Substitute, so go back to Twist Mountain then. The TM is rather easy to get. If you go outside where all the snow is, there are a few new cavern entrances. Go in one in the top left on the area. You will come to a maze like area. Next to the trainer after entering, you will see an item to the left. This is Substitute. Go foward and then right, beat the trainer, go down the steps and get your TM!

While your there, through another entrance at the top left, there is a "path" with a guy facing the wall. Talk to him, and he will give you A Pokemon Fossil which you can turn into a Pokemon at the Nacrene City Museum/Gym.

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I never knew that! What fossils does he give you, and what pokemon do they turn into?
Actually, he gives you a random one out of all the fossil Pokemon from every generation!
(And remember that this is daily!)
what sam means is, any fossil from past generations. I already knew the fossil thing. BTW, Sam, why would you know this if you don't even have access to B/W?
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Substitute is only available in Twist Mountain in winter, and it's not exactly hidden but the location is hard to explain with just text. This tutorial has step-by-step screenshots leading to the TM. So if you need help that should guide you the whole way.

Additionally, below is a screenshot of the TM's exact location in Twist Mountain.

(Source: Guide Strats)

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