A series of copolymers of dicyclohexyl itaconate (DCHI) and propylene oxide (PPO) were prepared by using peroxycarbamates as radical initiators for DCHI. The DCHI content in the copolymers was found to be very similar to that in the feed. The molecular weights of the copolymers prepared showed an inverse relationship with weight per cent of peroxycarbamates in samples with polydispersities between 1.3 and 2.2. The copolymers were characterized by chemical and physical methods, and their thermal stabilities were tested. The results from thermogravimetric analysis revealed two different thermal decomposition temperatures with two different activation energies.