A series of complexes consisting of natural amino acids and tin were developed as a new class of cost-effective catalysts with high reactivity and low toxicity towards some biocompatible aliphatic polyesters. The results demonstrated that Sn(AA)2 catalysts, especially the phenylalanine-tin complex (Sn(L-Phe)2) (Mn, up to 194 kg/mol), were suitable for the synthesis of moderate- and high-molecular-weight poly(L-lactide), which exhibited good biocompatibility.