Electrospinning technique is widely used to fabricate nanofibrous membranes mimicking the extracellular matrix structure. The utilization of synthetic polyvinyl alcohol (PVA) as the base material to construct electrospun nanofibers is often related to the limitation of biological function. Therefore, in this study, elastin (EL), a natural polymer, was incorporated into PVA matrix to overcome the biofunctional limitation. The ideal electrospinning parameters for the fabrication of PVA/EL electrospun nanofibers were investigated by varying the compositions of PVA/EL at 9.9/0.1, 9.5/0.5 and 9.0/1.0 (v/v) and the applied voltages at 18, 20 and 22 kV. With the increasing voltage from 18 to 22 kV, the mean fiber diameter decreased for the PVA and PVA/EL of 9.9/0.1 (v/v) while a fluctuating trend was observed for the 9.5/0.5 and 9.0/1.0 (v/v). The homogenous nanofibers construction with no beads was observed in the PVA/EL 9.5/0.5 (v/v). Both PVA and PVA/EL nanofibrous membranes displayed hydrophilicity with water contact angles below than 90°. In conclusion, the PVA/EL 9.5/0.5 (v/v) fabricated at 20 kV, possessed the ideal fiber morphology and wettability, to be subjected for biomedical applications.