Polyisocyanates of 2-[4-(4-nitrophenylazo)-N-ethylphenyl amino]ethoxy carbonyl amino hexyl isocyanate, DR1NCO, and (s)-(-)-2-methyl-1-butyloxy carbonyl amino hexyl isocyanate, MBI, were synthesized by anionic polymerization using sodium naphthalenide as an initiator in THF at -98 degreesC. In the polymerization reaction, crown ether (15C5) and octyl isocyanate (Oct-NCO) were used to suppress side reactions such as backbiting or chain transfer reaction. In the homopolymerization of DR1NCO, the polymers with high yield (similar to 94%) were obtained due to suppression of backbiting by 15C5. In the random copolymerization of DR1NCO with MBI. the chain transfer reaction was suppressed due to the low reactivity of anionic chain end induced by octyl isocyanate. The random copolymers showed the optical activity in CD and ORD measurements, and specific rotations increased with increasing the component of MBI.