A series of poly (vinyl alcohol) (PVA)/functionalized graphene oxide (FGO) nanofibers with low feeding ratios of FGO to PVA were fabricated by electrospinning method. In this study, the prepared PVA/FGO nanocomposites were dispersed in water phase followed by electrospinning treatment under different operational parameters (i.e., applied voltage, feeding rate and FGO contents) to give nanofibers of various diameters and morphologies. The morphology, diameter and structure of electrospun nanofibers and FGO were investigated by Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), (TGA) and differential scanning calorimetry (DSC). SEM images showed that the morphologies of the nanofibers were improved by the incorporation of FGO at a low loading content (e.g., 0.1~0.5 wt %) as compared to pure electrospun PVA. The crystallinity and thermal stability of PVA/FGO nanofibers were also studied.