The cationic homopolymerization and copolymerization Of L,L-lactide and epsilon-caprolactone in the presence of alcohol have been studied. The rate of homopolymerization of e-caprolactone is slightly higher than that Of L,L-lactide. In the copolymerization, the reverse order of reactivities has been observed, and L,L-lactide is preferentially incorporated into the copolymer. Both the homopolymerization and copolymerization proceed by an activated monomer mechanism, and the molecular weights and dispersities are controlled {number-average degree of polymerization= ([M](0) - [M](t))/[I](0), where [M](0) is the initial monomer concentration, [M], is the monomer concentration at time t, and [I](0) is the initial initiator concentration; weight-average molecular weight/number-average molecular weight similar to 1.1-1.3}. An analysis of C-13 NMR spectra of the copolymers indicates that transesterification is slow in comparison with propagation, and the microstructure of the copolymers is governed by the relative reactivity of the comonomers. (c) 2006 Wiley Periodicals, Inc.