Zn(OAc)(2)center dot 2H(2)O is found robe an effective bulk polymerization catalyst for the ring-opening polymerization of rac-lactide, L-lactide, epsilon-caprolactone and delta-valerolactone. The propensity of polymerizations can be enhanced by performing them in the presence of appropriate amounts of different alcohols. The major initiation pathway in the polymerization is found to proceed via the activated monomer mechanism and depending on the nature of the alcohol used, polymers with different end groups can be synthesized. These polymerization system constitutes an economical process, employing readily available inorganics such as Zn(OAc)(2)center dot 2H(2)O as catalyst and do not necessitate solvents. The overall system is green and eco friendly. (C) 2010 Elsevier B.V. All rights reserved.