PLLA microparticles were successfully fabricated via pulsed-DC electrospray. In this study, we investigated the effect of the pulsed voltage characteristics (e.g. pulse frequency, pulse amplitude and pulse width) on the particle’s size. We found that pulse frequency, pulse amplitude, pulse width, and the combinations of these factors had a statistically significant effect on the particle’s size. The process conditions to obtain smaller particles with uniform shape and size are a low pulse frequency, high pulse amplitude, and long pulse width (or a high duty cycle).