var wireMat:WireframeMaterial = new WireframeMaterial(0xCCCCFF);
var colorMat:ColorMaterial = new ColorMaterial(0x00FFCC);
var compMat:CompositeMaterial = new CompositeMaterial();
compMat.addMaterial(wireMat);
compMat.addMaterial(colorMat);

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Quick & easy way to add multiple materials to a single object.

Composite Materials in PV3D (Multiple Materials On One Object)

ActionScript 3