The surface chemical analyses of a series of colloids based on poly(methyl methacrylate) and poly(4-vinylpyridine) have been carried out using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The colloids were prepared by the vinyl polymerization of monomers bearing the reactive functional groups hydroxyl, amide, and epoxide. XPS and TOF-SIMS provided complementary information on the functional groups at the colloid particle surfaces and gave good correlation with electrophoretic mobility and particle size data. This paper demonstrates the capability of these surface analysis techniques for studying the complex surface chemistries of copolymer colloid systems.