AbstractPolymerization of 1,3‐dioxolane (1) with terephthaloyl ditriflate as initiator in dichloromethane at −40°C produces poly(1)s with molecular weights given by {([Monomer]0‐ [Monomer]e)/([Initiator])} ([Monomer]e= monomer conc. at equilibrium). Termination with triethylamine leads to poly(1)s with two quaternizeda‐aminoether functions as end groups. These end groups react with carboxylate ions in apolar solvent to form the corresponding hemiacetal esters. This reaction sequence allows to produce a variety of well defined poly(1) tel