Methyl methaerylate/1,2-divinylbenzene (MMA/DVB) in an opaque emulsion were successfully grafted onto the surface of polymeric substrate under the irradiation of UV light with benzophenone (BP) as a photoinitiator that was previously coated on the substrate surface. Monomer conversion, grafting efficiency, and grafting yields were determined by the gravimetric method. ATR-IR, AFM, and TEM were used to characterize the surface composition, to observe the topography of the grafted substrates, and to view inter-film colloid particles formed by cross-linking. The results reveal that, with the opaque MMA/DVB emulsion system and CPP film as substrate, the monomer conversion is in the range of 15-55%, the grafting efficiency is about 80%, the grafting yield reaches 5%, and the thickness of the graft layer can be controlled in the range 0.09-1.5mum. Images of AFM show that the graft layer is pilled up by nanoparticles (about 30-50 nm in diameter), which are linked together and tied to the substrate surface with covalent bonds. A possible model of surface graft polymerization including surface initiating, nucleation, and shish kebab growing is put forward to interpreting the above results.