We have investigated anionic polymerization ability of N-substituted maleimides (RMI) with various amines as anionic initiator. As a result, anionic polymerizations of RMI proceed successfully in high polar solvents such as DMF and DMSO. The basicity and structure of amines influenced yields and number average molecular weights of polymers. Furthermore, using various chiral amines as an initiator, polymerizations of RMI were performed to obtain optically active polymers.