We investigate the formation of ultrathin nanofibers (UNFs) with diameters below 20 nm by electrospinning Nylon-6 solution with various processing parameters. It is found that the UNF density and morphology are highly dependent on the solution concentration and age, collecting distance, and ambient humidity. The sequence that ribbon-like fibers are stretched by the electric force, followed by rapid phase separation of the splitting film is proposed as a formation mechanism of the UNFs. Based on the morphological study, a model of hexagonal nets is developed in order to estimate the filtration efficiency by the UNF structure. The estimated efficiency due to the UNFs is then combined with the contribution from the un-split nanofibers (NFs) to compute the total filtration efficiency and pressure drop for each of the electrospun media by applying a layered multiple zone model. The filtration performance of the electrospun media against nanoparticles is evaluated using the quality factor and specific filtration performance index, weighed against the pressure drop and basis weight of the media, respectively. Our results show UNFs are advantageous when high filtration efficiency is required and low weight is desired and/or little space is available for the filter media.