faces = First@Normal@PolyhedronData["Dodecahedron", "Faces"];
colors = Table[ColorData[97, i], {i, 12}];
Graphics3D@Riffle[colors, faces]

myVertices = N@PolyhedronData["Dodecahedron", "Vertices"];
myFaceIndices = PolyhedronData["Dodecahedron", "Faces"];
mycolors = {Red, Orange, Yellow, Green, Blue, Orange, Black, White,
   Purple, Green, Red, Yellow};
Graphics3D@
 Transpose[{mycolors, (Polygon[myVertices[[#]]] & /@ myFaceIndices)}]