Stable poly(styrene-co-divinylbenzene) [P(St-co-DVB)] microspheres with narrow size distribution were synthesized in the presence of 2,2'-azobis(2,4-dimethyl valeronitrile) (V-65) and co-initiator in an acetone/water mixture in the precipitation polymerization at 53 ℃ for 24 h. Potassium peroxodisulfate (KPS), ammonium peroxodisulfate (APS) and sodium peroxodisulfate (NaPS) were used as co-initiators. The optimum ratio of acetone to water for the formation of a narrow distribution of P(St-co-DVB) particles was 49:11 (g/g). The optimum co-initiator compositions for narrow distribution were 9:1 (g/g) for V-65 to KPS, 11:1 for V-65 to APS and 6:1 for V-65 to NaPS. The yield for these compositions was 54~57% and the largest particle size was obtained with the lowest zeta-potential and CV values. From the XPS measurements, the charge density was increased but the zeta potential decreased with increasing sulfur content, implying that the sulfate group provides the electrostatic stabilization on the particle surface. This suggested that the self-crosslinking between styrene and DVB, the electrostatic stabilization of initiators, and the balanced hydrophobic and hydrophilic properties of the solvents are responsible for the formation of stable P(St-co-DVB) spherical particles with narrow size distribution.