Carboxylic-acid-initiated ring-opening polymerization (ROP) of epoxides is a fast approach to esterified polyethers which are cleavable at the termini or centers. A major challenge lies in conventional ROP methods because of the lability of ester groups formed in the initiation step. Here, we describe chemoselective ROP of epoxides from aliphatic, aromatic, and methacrylic carboxylic acids using two-component metal-free catalysts. Transesterification is clearly absent so that well-defined α-(carboxylic ester)-ω-hydroxy polyethers are generated in one step from monocarboxylic acids. The livingness of the ROP is verified despite the slow initiation mode. The ester end group can be readily cleaved from the polyether hydrolytically. An α,ω-dihydroxy poly(propylene oxide) with two central ester groups is generated from a diacid initiator and transformed in situ by the same catalyst to polyurethane which shows distinct enzymatic degradability. This study provides convenient access to α,ω-heterobifunctional polyethers with cleavable, releasable, or modifiable end groups and to biodegradable polyether-based materials.