This study investigated the possibility of using styrene, a weak donor forming donor(D)/acceptor(A) pairs with electron-poor (EP) vinyl monomers, for initiating spontaneous photopolymerization and photografting of the copolymers onto polypropylene. Maleic anhydride (MA), methyl methacrylate (MMA), methyl acrylate (MAC), dimethyl maleate (DMMA), acrylonitrile (AN) and acrylic acid (AA) were the EP monomers used. Grafting yields together with FTIR analyses were used to confirm the presence of grafting. Styrene/MMA and styrene/AN systems achieved significant grafting, but such levels of grafting were not observed in the styrene/MAC and styrene/DMMA systems. No grafting was observed for styrene/AA or styrene/MA systems, but the latter system underwent photopolymerization. The effect of solvents on grafting was evaluated on styrene/MMA and styrene/AN systems and dimethylformamide (DMF) was found to retard grafting of both D/A systems. In contrast, chloroform and methanol enhanced grafting of the styrene/AN system although these two solvents had no significant effect on the grafting of the styrene/MMA system.