Electrospinning is an efficient method of producing nanofibers out of polymers that shows a great potential for the filtration territory. Featuring water-soluble chitosan (WS-CS), a low-pollution process and a self-made needleless machine, PVA/WS-CS nanofibrous membranes were prepared and evaluated for nanofiber diameter, bacteriostatic property, filtration efficiency, pressure drop, and quality factor. Test results indicate that the minimal fiber diameter was 216.58 ± 58.15 nm. Regardless of the WS-CS concentration, all of the PVA/WS-CS nanofibrous membranes attained a high porosity and a high water vapor transmission rate (WVTR), with a pore size of 12.06–22.48 nm. Moreover, the membranes also exhibit bacteriostatic efficacy against Staphylococcus aureus, an optimal quality factor of 0.0825 Pa−1, and a filtration efficiency as high as 97.0%, that is 72.5% higher than that of common masks.