In this study, electrospun reduced graphene oxide (rGO) and poly(vinyl alcohol) (PVA) nanocomposites were developed with the concentration of rGO as 0.5 and 1.0 wt% by dispersing rGO in the PVA solution without using any co-solvent which may cause toxic effect for possible applications like packaging and tissue engineering. Water solubility of PVA was eliminated by UV-radiation crosslinking method. SEM analysis proved that continuous and bead-free nanofibers were obtained by electrospinning process and all electrospun mats had similar fiber characteristics with homogeneous fiber morphology. The average fiber diameter (nm), inter-fiber pore size (μm) and the porosity (%) were increased with rGO incorporation. Additionally, enhanced tensile properties was achieved by rGO addition as the highest tensile strength was obtained as ∼5 MPa for electrospun PVA + 1.0 wt% rGO nanocomposites. ATR-FTIR analyses showed that there was a relatively strong interfacial interaction between rGO and PVA. Moreover, the thermal stability of obtained nanocomposites was enhanced by rGO addition without changing the crystal structure of PVA proved by XRD analyses. Also, improved electrical conductivity of the nanocomposites was obtained by rGO content as the highest conductivity (∼11 μS · cm-1) was measured for electrospun PVA + 1.0 wt% rGO.