A series of novel chiral propene oxides bearing substituted N,N-diphenylamino moiety were synthesized and anionically polymerized. Most of propene oxides gave polymers possessing high specific rotation and intensive circular dichroism (CD) signals, which were attributed to the helical conformation of the main chain. Poly(3-(4,4'-dimethoxy)diphenylaminopropene oxide) exhibited the highest specific rotation ([alpha](365)(20) = -5400).