In the present study, a new class of biodegradable graft copolymers of polystyrene (PS) with aliphatic polyester (APE) side chains were synthesized through combination of nitroxide-mediated free radical polymerization (NMRP) and ring-opening polymerization (ROP) with copper (I)-catalyzed click' chemistry. First, the click component, azido-functional PS (PS-N-3) was prepared by copolymerization of styrene and chloromethyl styrene by NMRP followed by the conversion of chlorine groups of the resulting copolymer to azido groups by using NaN3 in N,N-dimethylformamide. Propargyl functional APEs were prepared independently by ROP of lactic acid and glycolic acid using tin octoate in the presence of propargyl alcohol at 130 degrees C. Finally, PS-N-3 was coupled with the resulting polymers by click chemistry to yield graft copolymers (PS-g-poly (L-lactic-co-glycolic acid) [PLLA] and PS-g-PLLGA, respectively). The intermediates and final graft copolymers were characterized by proton nuclear magnetic resonance (H-1 NMR) and Fourier transform infrared spectral and gel permeation chromatography analyses. The hydrolytic degradation behavior of the obtained graft copolymers in phosphate buffer saline solution were investigated by the weight loss and molecular weight measurements. It is shown that both copolymers undergo slow hydrolytic degradation, PS-g-PGLLA being relatively faster due to the presence of hydrophilic glycolic acid groups in the structure.