Polystyrene microspheres were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2-methoxy ethanol. Surface characterization of the formed particles was performed by x-ray photoelectron spectroscopy and critical surface tension measurements. The influence of different reaction parameters, i.e., monomer concentration, stabilizer type (polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinylacetate and polyvinylacetate), stabilizer concentration and molecular weight, and initiator type and concentration, on the molecular weight and on the size and size distribution of the formed polystyrene microspheres was investigated. The correlation between the surface composition and wettability properties of the particles surface and their size and size distribution was also demonstrated.