Polymeric microparticles have been shown to have great impacts in the area of drug delivery, biosensing, and tissue engineering. Electrospray technology, which provides a simple yet effective technique in the creation of microparticles, was utilized in this work. In addition, altering the electrospray experimental parameters such as applied voltage, flow rate, collector distance, solvents, and the polymer-solvent mixtures can result in differences in the size and morphology of the produced microparticles. The effects of the flow rate at (0.15, 0.3, 0.45, 0.6, 0.8, and 1 mL/h) and N, N-Dimethylformamide (DMF)/acetone solvent ratios (20:80, 40:60, 60:40, 80:20, 100:0 v/v) in the production of polyvinylidene fluoride (PVDF) microparticles were studied. Scanning electron microscopy (SEM) was used to observe changes in the morphology of the microparticles, and this revealed that a higher acetone to DMF ratio produces deformed particles, while flow rates at (0.3 and 0.45 mL/h) and a more optimized DMF to acetone solvent ratio (60:40 v/v) produced uniform spherical particles. We discovered from the Raman spectroscopy results that the electrosprayed PVDF microparticles had an increase in piezoelectric β phase compared to the PVDF pellet used in making the microparticles, which in its original form is α phase dominant and non-piezoelectric.