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The surface energy control capability of electrohydrodynamic force provides electrospraying with various potential advantages such as simple particle size control, mono-dispersity, high recovery, and mild processing conditions. Herein, particle fabrication of biodegradable polymers using electrospraying was developed. The major processing parameters such as the conductivity of spraying liquids, flow rate, etc., were examined to obtain the successful apparatus configuration of electrospraying. The choice of a consolidation medium was critical in obtaining well-dispersed nanoparticles. When triphenylphosphate aqueous solution was employed as a consolidation medium, its concentration was not an effective parameter to control the aggregation of primary particles. When organic solvents were employed, the processing windows of electrospraying were relatively narrow than water-based systems.