Kinetically controlled ring-expansion polymerizations (REPs) are defined syntheses generating cyclic oligomers and polymers without linear intermediates and without equilibration reactions. This review reports syntheses of cyclic metal alkoxides and their use as initiators for REPs of lactones, cyclic diesters, and cyclocarbonates. In addition to homopolyesters. telechelic oligoesters or polyesters. random copolyesters, and A-B-A triblock copolymers can be prepared by these REPs. The in situ combination of REPs with condensation (mostly acylation) reactions allows a broad variation of end groups. The in situ combination of REPs with polycondensation enables various chain-extension reactions, including the syntheses of multiblock copolymers. With spirocyclic initiators, four-armed stars with functional end groups may be prepared. The in situ combination of REPs with condensation reactions of trifunctional or multifunctional reagents makes a broad variety of networks accessible. The average segment lengths may be controlled via the monomer/initiator ratios of the REP. All materials produced via the aforementioned REP processes are biodegradable and nontoxic, and this allows for biomedical and pharmaceutical applications. (C) 2004 Wiley Periodicals, Inc.