Has there ever been a Pokemon that used Substitute in the anime?

Question

Not sure what it would look like or how it would work physically...

Answer 1

Lila's Delcatty in Battling the Generation Gap!
The Wild Togepi in Where No Togepi Has Gone Before!
Professor Juniper's Accelgor in Evolution Exchange Excitement!
Shaymin (land form) in Giratina and the Sky Warrior
Generally speaking, it makes an exact copy of the user (an afterimage) and once the copy is hit it dissapears.

Comments

http://bulbapedia.bulbagarden.net/wiki/Substitute_(move)#In_the_anime

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Ah I see; that makes more sense now. I saw the evil Togepi episode and didn't even realise it was using substitute.