The photopolymerization of methylmethacrylate induced by pyrene, 1-acetylpyrene (AP), and 1-(bromoacetyl)pyrene (BP) has been investigated. Under all conditions employed, pyrene was completely ineffective. Introduction of a carbonyl and a bromo group in pyrene enhanced the polymerization efficiencies. Efficiency of AP as photoinitiator was very low; however, BP was proved to be a good photoinitiator. The polymerization with BP follows first-order kinetics with respect to monomer conversion, with a shorter induction period as compared with that of AP. The value of the initiator exponent (0.5) and the linear dependence of reciprocal average degree of polymerization on the square root of the initiator concentration suggest radical polymerization with bimolecular termination. IR and NMR spectra showed the atactic nature of polymethylmethacrylate. (c) 2005 Wiley Periodicals, Inc.