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Greninja gets both Mat Block and Water shuriken, Delphox and Chesnaught just get 1 signature move, Spiky Shield (Chesnaught) and Mystical Fire (Delphox). I know Mat Block isn't "technically" a signature move, but it's the only one that learns it. Thanks!

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Unknown, you would have to ask Game Freak themselves. Mat Block isn't part of the Kalos Starter Trio's signature moves though. Game freak sometimes do weird things. Like Slowpoke Learning Flamethrower and Yanmega not able to learn fly even when it's pokedex says it can carry an adult.

Edit: Mat Block is now Greninja's only Pokemon-specific move. In fact, the all of Kalos Starter Trio specific moves can now be learned by another Pokemon. (Mystical Fire: Mismagious, Water Shuriken: Accelgor, and Spiky Shield: Maractus/Cacturne)

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I never understood the Slowking and Slowbro learning Flamethrower...
hey u know why greninja has to sig moves? cause hes the best kalos starter
greninja might also have two signature move because he is the primary starter in the show
A signature move doesn't mean that only that pokemon can learn it! Would you consider keniesis alakazam's signature move? No other pokemon gets it. Most anime viewers would consider thunderbolt pikachu's signature move, especially now that it has no volt tackle. It's just the move we remember them for, that is and/or goes with their theme, and that is usually just how gamefreak tries to embody the unique abilities mentioned in the pokemon's 'Dex entry. Okay?
Signature moves is probably just one of those terms that can have multiple meanings.