Chiral (S)-(-)-N-1-cyclohexylethylmaleimide [(S)-CEMI] and (R)-(+)-N-1cyclohexylethylmaleimide [(R)-CEMI] were synthesized successfully and then polymerized with chiral complexes of (-)-sparteine or (SS)-(1-ethylpropylidene)bis(4-benzyl-2-oxazoline) [(SS)-Bnbox] and organometal as initiators in toluene or tetrahydrofuran to obtain optically active polymers. The effects of the polymerization conditions on the optical activity and structure of poly(N-1-cyclohexylethylmaleimide)s were investigated with gel permeation chromatography, circular dichroism, specific rotation, and C-13 NMR measurements. Poly[(R)-CEMI] obtained with dimethylzinc (Me2Zn)/(SS)-Bnbox had the highest specific rotation ([alpha](435) = +323.7degrees). Complexes of Bnbox and diethylzinc or Me2Zn were used very effectively as chiral initiators for the asymmetric anionic polymerization of (S)-CEMI and (R)-CEMI. (C) 2004 Wiley Periodicals, Inc.