In order to create a functionalized biodegradable polymer for vascular tissue engineering application, poly(DL-lactide-co-RS-β-malic acid) (PDLLMAc) was synthesized. PDLLMAc was obtained after hydrogenolysis of poly(DL-lactide-co-RS-β-benzyl malolactonate) (PDLLMA), which was from the ring-opening polymerization of DL-lactide (DLLA) and RS-β-benzyl malolactonate (MA) using stannous octoate as catalyst. The copolymers were characterized by 1H-NMR, FTIR, GPC and DSC. The tensile strength and water uptake of the copolymers were measured. In copolymerization, the proportion of MA in the derived copolymers was lower than that in the feeding dose, a consequence of its lower reactivity. The molecular weight of the copolymers decreased with increasing MA content. The protective benzyl groups were completely removed in hydrogenolysis. The glass transition temperature (Tg) of the protected copolymers decreased with increasing MA content. The mechanical strength test showed that the tensile strength of PDLLMA decreased while elongation increased with MA content increasing, and the tensile strength increased and elongation decreased with increasing malic acid content in PDLLMAc for the formation of hydrogen bonding. The water uptake showed that more hydrophilic malic acid adsorbed more water in PDLLMAc. In order to test the reactivity of functional pendant groups, bioactive RGD peptide was immobilized on the functionalized polymer film surface and smooth muscle cells (SMCs) were cultured on it. The results showed that the functionalized copolymer was biocompatible and could be potentially applied in vascular tissue engineering.