A kind of N-substituted maleimide (RMI), chiral (S)-N-maleoyl-L-leucine propargyl ester ((S)-PLMI) with a specific rotation of [alpha](435) = -27.5 degrees was successfully synthesized from maleic anhydride, L-leucine, and propargyl alcohol. (S)-PLMI was polymerized by three polymerization methods to obtain the corresponding optically active polymers. Asymmetric anionic, radical, and transition-metal-catalyzed polymerizations were carried out using organometal/chiral ligands, 2,2'-azobisisobutyronitrile (AIBN) and (bicyclo [2,2,1]hepta-2,5-diene) chloro rhodium (1) dimer ([Rh(nbd) Cl](2)), respectively. Poly((S)-PLMI) obtained by [Rh(nbd)Cl]2 in DMF showed the highest specific rotation of -280.6 degrees. Chiroptical properties and structures of the polymers obtained were investigated by GPC, CD, IR, and NMR measurements. Two types of poly((S)-PLMI)-bonded-silica gels as the chiral stationary phase (CSP) were prepared for high-performance liquid chromatography (HPLC). Their optical resolution abilities were also elucidated. (C) 2007 Wiley Periodicals, Inc.