High-molecular-weight PTeMC and PHMC were prepared by the lipase-catalyzed polymerization of butane-1,4-diol or hexane-1,6-diol and diphenyl carbonate via the formation of a cyclic dimer by a green process. Cyclic carbonate dimers were prepared by the lipase-catalyzed condensation of diphenyl carbonate with butane-1,4-diol or hexane-1,6-diol in dilute toluene solution using an immobilized lipase from Candida antarctica, and was followed by the ring-opening polymerization of the cyclic dimer in bulk with the same lipase to produce PTeMC with M(w) = 119 000 g . mol(-1) and PHMC with M(w) = 399 000 g . mol(-1), respectively. Additionally, enzymatic polymerization of cyclic carbonate dimer was analyzed with respect to the K(m) and V(max) for the lipase.