In this study, we have showed a facile route for fabrication of a novel microporous material based on chitosan (CS) and poly(vinyl alcohol) (PVA) biodegradable nanofibers that have high specific surface area, considerable porosity, and small diameter. Scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, fourier transform infrared spectroscopy, Brunauer-Emmett-Teller surface area analysis, and CHNS/O elemental analyser were applied to characterize the fabricated CS/PVA composite nanofibers. Moreover, the influences of spinning conditions including concentration, voltage, electrospinning distance, and flow rate, on size distribution and pore diameter of the final product were systematically studied using 2(k-1) factorial design experiments, and the response surface optimization was used for determining the best synthesis parameter. The results obtained from 2(K-1) factorial design experiments showed that electrospinning parameters influenced the size distribution and pore diameter of the CS/PVA microporous material. Based on the response surface methodology, the CS/PVA product could be obtained with a high microporous diameter of 1.8 nm and a small diameter distribution of 15.0 nm under optimized conditions. The obtained results showed that the fabricated samples could be utilized in different applications.