In this paper, a novel electrostatic-assisted melt blown process was reported to produce polypropylene (PP) microfibers with a diameter as fine as 600 nm. The morphology, web structure, pore size distribution, filtration efficiency, and the stress and strain behavior of the PP nonwoven fabric thus prepared were characterized. By introducing an electrostatic field into the conventional melt-blown apparatus, the average diameter of the melt-blown fibers was reduced from 1.69 to 0.96 μm with the experimental setup, and the distribution of fiber diameters was narrower, which resulted in a filter medium with smaller average pore size and improved filtration efficiency. The polymer microfibers prepared by this electrostatic-assisted melt blown method may be adapted in a continuous melt blown process for the production of filtration media used in air filters, dust masks, and so on.