Poly(ethylene-co-vinyl acetate)(EVA) microspheres were prepared by a thermally induced phase separation. The microsphere formation occurred by the nucleation and growth mechanism in the metastable region. The diluent used was toluene. The microsphere formation and growth was followed by the cloud point of the optical microscope measurement. The microsphere size distribution, which was obtained by SEM observation and particle size analyzer, became broader when the polymer concentration was higher, the content of vinyl acetate in EVA copolymer was higher, and the cooling rate of EVA copolymer solution was lower.