A novel dispersion copolymerization of maleic anhydride (MAn) and vinyl acetate (VAc) without adding stabilizer is developed, which gives uniform copolymer microspheres with tunable sizes. Some principal factors affecting the microspheres, such as reaction time, monomer concentration and feed ratio, reaction media, and cosolvent, were investigated. It was found that the stabilizer-free dispersion copolymerization of MAn and VAc is a rapid process, and the particle size grows in accordance with the evolution of polymerization. The chemical composition of the copolymer microspheres was characterized by FT-IR and C-13 NMR spectroscopies. Over a wide range of monomer concentrations, the microspheres can always be formed and stably dispersed, with uniform sizes ranging from 180 nm to 740 nm. The yield of copolymer microspheres reaches a maximum at 1:1 feed ratio of MAn to VAc, owing to the alternating copolymerization between the binary monomers by a known charge-transfer-complex mechanism. However, the diameter of microspheres drastically increases when MAn content is enhanced. Only some specific alkyl ester solvents, such as n-butyl acetate, isobutyl acetate, n-amyl acetate, are desirably fit for this unique stabilizer-free dispersion polymerization. Furthermore, we found that when some acetone is added as a cosolvent, the copolymer microspheres can still be formed, with much larger diameters. (c) 2005 Wiley Periodicals, Inc.