Electrospun nano-web structures (ENWSs) were successfully fabricated from ionized binary solution of cellulose(Mn30)/polyethylene oxide(Mn200) (CA/PEO of 0.5-1.5). Final concentration of polymers was 12% (w/v) in the solution, and lithium chloride was used as ionizing agent. Response surface methodology (RSM) was applied to the optimize fabrication of ENWSs. Results of multiple linear regression analysis revealed that the solution properties and ENWSs morphology were strongly influenced by CA/PEO. An increase in PEO amount increased the viscosity which is a function of molecular weight, and as a result raised the entanglement of polymeric solution but decreased the surface tension that all support nanofibers fabrication. The size of nanofibers decreased with reducing PEO and LiCl concentration. Increasing the content of LiCl promoted the electrical conductivity (EC) value; however, junction zones were formed. The overall optimum region was found to be at combined level of 1.5% CA/PEO and 0.49% (w/v) LiCl. (C) 2014 Elsevier Ltd. All rights reserved.