Asymmetric anionic homopolymerizations of N-1-naphthylmaleimide (1-NMI) were performed with chiral ligand/organometal complexes to form optically active polymers. Poly(1-NMI)s obtained with methylene-bridged bisoxazoline derivatives (Rbox)-diethylzinc (Et2Zn) complexes showed high specific optical rotations ([alpha](435)(25)) from + 152.3 to + 191.4 degrees. Circular dichroism spectra of the polymers exhibited a split Cotton effect in the UV absorption-band region. According to the exciton chirality method, the absolute configuration of the polymer main chain was determined according to the following method: (+)-poly[N-substituted maleimides (RMI)] main chains can contain more (S,S)- than (R,R)-configurations. (-)-Poly(RMI) main chains can contain more (RR)- than (S,S)-configurations.