Model of a video-game and movie hero - Pikachu, a yellow cute) Everyone, who watched a movie or only heard about Pokemons, knows him.
In the Edit mode you can choose for every face a material. First, you choose faces, then creating material and Apply them to those faces.
https://blender.stackexchange.com/questions/516/add-different-materials-to-different-parts-of-a-mesh
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