Optically active homopolymers and copolymers, bearing chiral units at the side chain and end chain, were prepared via atom transfer radical polymerization (ATRP) techniques. The well-defined optically active polymers were obtained via the ATRP of pregnenolone methacrylate (PR-MA), beta-cholestanol acrylate (CH-A), and 20-(hydroxymethyl)-pregna-1,4-dien-3-one acrylate (HPD-A) with ethyl 2-bromopropionate as the initiator and CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine as the catalytic system. The experimental results showed that the polymerizations of PRMA, CH-A, and HPD-A proceeded in a living fashion, providing pendent chiral group polymers with low molecular weight distributions and predetermined molecular weights that increased linearly with the monomer conversion. Furthermore, the copolymers poly(pregnenolone methacrylate)-b-poly[(dimethylamino)ethyl methacrylate] and poly(pregnenolone methacrylate-co-methyl methacrylate) were synthesized and characterized with H-1 NMR, transmission electron microscopy, and polarimetric analysis. In addition, when optically active initiators estrone 2-bromopropionate and 20-(hydroxymethyl)-pregna-1,4-dien-3-one 2-bromopropionate were used for AMPS of methyl methacrylate and styrene, terminal optically active poly(methyl methacrylate) and polystyrene were obtained. (c) 2006 Wiley Periodicals, Inc.