AbstractCationic ring‐opening copolymerizations of various cyclic ether compounds with volume expanding monomers bearing norbornene backbones [norbornene‐spiro orthocarbonate (N‐SOC) and norbornene‐cyclic carbonate (N‐CC)] were carried out in the presence of a thermally latent initiator 1. The 10% weight loss decomposition temperatures (Td10) and the volume changes on the copolymerizations were measured for these resultant products. In the comparison between copolymerizations of bifunctional epoxide 2 with N‐SOC and with N‐CC, it was found that N‐CC served as a more useful volume controllable comonomer than N‐SOC. The copolymerizations with N‐CC yielded the products with a decrease in the volume change (volume shrinkage) and with an increase in the monomer feed ratio of N‐CC; Td10 was relatively similar to the homopolymer of epoxide 2 and was observed except when the proportion of N‐CC was more than 20% in the monomer feed ratio of N‐CC. In contrast, similar copolymerizations with N‐SOC did not exhibit such tendencies, probably because of the low efficiency of the copolymerization derived from the low miscibility of N‐SOC for the epoxide. The other copolymerization systems of other bi‐ and monocyclic ether compounds (3–6 and phenyl glycidyl ether) with N‐CC also indicated an almost similar tendency toward that of the copolymerization with epoxide 2. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5113–5120, 2004