Electrospraying technology has been studied in many fields to produce particles of various substances from nanoscale to microscale sizes. Unlike pure liquids, droplets formed by electrospraying that are comprised of polymer solutions undergo additional solidification processes involving solvent evaporation, which primarily determine the particle size and morphology. Herein, the effects of the solvent properties on the morphology and dimensions of solidified particles were systematically studied. In general, the size of the solidified spherical particles with smooth surfaces reflected that of the initially formed liquid droplets, which could partially be estimated by theoretical equations developed for pure liquids. Particle sizes increased with an increase in polymer content and a decrease in the boiling point of the volatile solvent. Inhomogeneous drying processes related to phase separation or skin formation resulted in hollow, cuplike, and porous particle structures, with particle sizes and morphologies that were outside of the scope of the theoretical treatments. The selection of a proper solvent or solvent mixture seemed to be a convenient way to control the particle morphologies, such as hollow, cuplike, or porous structures. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 430-437, 2009