Polymerizations of chiral or achiral N-substituted maleimides (RMI) have been systematically studied by the authors In this study, the polymerizations of (S)-N-maleoyl-L-leucine propargyl ester ((S)-PLMI) having different reactive groups (olefinic and/or acetylenic group) were investigated in detail. Using n-BuLi, the yield of MeOH-H2O (7/3)-insoluble part in toluene was lower than that in THF, indicating that polar solvents were efficient to obtain higher yields. The number-average molecular weights (Mn) and specific rotations of the polymers obtained with organometal/chiral ligand complex were almost higher than those with only by n-BuLi. 1H NMR spectra showed that only olefinic groups in the maleimide ring reacted and that acetylenic groups were not converted. In radical polymerizations, the yield and the specific rotation of the polymer obtained in toluene were lower than in THF. The absolute values of specific rotation of polymers were much lower than those obtained by anionic polymerizations, suggesting that the asymmetric fields formed in the radical polymerization were less than those formed in the anionic polymerization. When the polymerization occurred in toluene, both an olefinicand an acetylenic group partly polymerized. In THF, the olefinic group entirely polymerized, while the acetylenic group partly polymerized. Polymerizabilities of (S)-PLMI using (bicyclo[2,2,1]hepta-2,5-diene)chlororhodium (I) dimer [Rh(nbd)Cl]2 as a catalyst and the specific rotation of polymers were strongly influenced by polymerization solvents. The FT-IR spectrum indicated that the acetylenic group was entirely polymerized. Chemoselective polymerizations of chiral (S)-PLMI having different reactive groups were possible by selecting suitable initiators, catalysts, and solvents.