Alkali metal carboxylates were discovered as efficient and simple catalysts for the ring-opening polymerization of cyclic esters that are alternatives to conventional metal-based catalysts and organocatalysts. In our system using an alcohol initiator and this simple catalyst, biodegradable and biocompatible aliphatic polyesters, such as poly(lactide), poly(epsilon-caprolactone), poly(delta-valerolactone), and poly(trimethylene carbonate), were obtained with predictive molecular weights ranging from 3500 to 22 600 and narrow dispersities. A kinetic experiment for the ROP of L-lactide confirmed the controlled/living nature of the present ROP system, which allowed the precise synthesis of end-functionalized polyesters as well as multihydroxyl-containing polyesters, including alpha,omega-hydroxy telechelic and star-shaped polyesters. Furthermore, a block copolymer containing the poly(L-lactide) segment was successfully synthesized using a macroinitiator possessing a hydroxyl group at the chain end. The tunability of the alkali metal carboxylates by the appropriate choice of the alkyl moiety and countercation enables not only control of the polymerization behavior but also expansion of the scope of the applicable monomers. Given the low cost, easy handling, and low toxicity of the alkali metal carboxylates, the present ROP system can be highly promising for both laboratory- and industrial-scale polyester productions.