The reactions of substituted (benzimidazolylmethyl)amines ligands (L1–L3) with ZnEt2 in the presence of either BnOH or t-BuOH afforded the corresponding Zn(II) metal alkoxides [Zn(L1)(OBn)]2 (1), [(Zn(L2)(OBn)]2(2), [Zn(L3)(OBn)]2 (3), [Zn(L2)(t-BuO)]2 (4), respectively. Complexes 1–4 formed effective initiators in the ring-opening polymerization (ROP) reactions of ɛ-caprolactone (ɛ-CL), D,L-lactide (D,L-LA) and L-lactide (L-LA). The ROP reactions followed pseudo-first-order kinetics with respect to monomer. Moderate molecular weight polymers of 10,650 g mol−1 exhibiting relatively narrow molecular weight distributions (1.16–1.54) were obtained. Predominantly crystalline isotactic poly(L-LA) and heterotactic poly(D,L-LA) were produced, respectively. Thermal analyses of PLA also supported the formation of isotactic poly(L-LA) with decomposition temperature of 298 °C.