Synthesis of graft copolymers by combination of atom transfer radical polymerization (ATRP) and photoinduced reaction of benzodioxinone was reported. First, statistical copolymers of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) were prepared by ATRP process. Then, the other component, namely benzodioxinone functional polystyrene (PS-B) was prepared independently by the etherification reaction of hydroxyl benzodioxinone (HDPD) with polystyrene (PS-Br) obtained by ATRP by using K2CO3 in acetone. Photolysis of poly(hydroxyethyl methacrylate-co-methyl methacrylate) (P(HEMA-co-MMA)) and (PS-B) pre-polymers in CH2Cl2 at lambda(inc) > 300 nm yielded graft copolymers. The graft copolymers and the intermediates were characterized in detail by using H-1 NMR, GPC, UV, FT-IR, DSC, and AFM measurements.