This study experimentally investigated the effect of different molecular weights of Poly vinyl acetate (PVAc) on electro-spinning ability of PVAc/DMAC sol-gels. The influences of polymer solution concentration and electrospinning process parameters (needle tip to collector distance, flow rate, and applied voltage) on the mean diameters of electrospun PVAc nanofibers were examined by design of the experiments based on the Taguchi method. Three levels were considered for each process factor as inputs for the Taguchi DoE technique. To characterize and optimize the mentioned parameters, Taguchi's L9 orthogonal design (four parameters, three levels) was used. The "smaller-the-better" approach was used to utilize the optimum production conditions based on the signal-to-noise (S/N) ratios. The results indicated that the polymer solution concentration was the most important parameter on the mean diameter of the nanofibers. The minimum nanofiber diameter at the optimum conditions was measured about 52 nm. In conclusion, the Taguchi DoE method was identified as an efficient technique to characterize and optimize the electrospinning process parameters to increase the robustness of nanofiber fabrication.