A novel bifunctional monomer, (4-maleimidophenyl)oxirane (MAPO), with very reactive maleimido and epoxy groups, was prepared through the selective oxidation of the two carbon-carbon double bonds of N-(4-vinylphenyl)maleimide. Either of the two different polymerizable groups (vinylene of the maleimide moiety and the mono-substituted epoxide) of MAPO was able to be selectively polymerized by choosing the polymerization method. For radical polymerization, MAPO gave poly{p-[1,2-(epoxyethyl)phenyl]maleimide} (PEPM) with dense pendent epoxy groups in 76% yield without cross-linking. MAPO also gave poly(maleimidostyrene oxide) (PMSO) with dense pendent maleimido groups through cationic polymerization in 60% yield. On the other hand, anionic polymerization with an of MAPO produced only insoluble gel-like materials due to unselective polymerization of the two polymerizable groups (Scheme 1). The vinylene group of the maleimide moiety in PMSO easily reacted with the mercapto group, and the ring-opening reaction of the epoxy groups in PEPM with amino groups took place. (C) 2009 Elsevier Ltd. All rights reserved.