A series of ultrafine polyvinyl alcohol (PVA)/graphene oxide (GO) nanofibrous scaffolds (PGNSs) with different GO content (0, 0.25, 0.5, and 1.0%) was fabricated via an electrospinning process. The morphology, composition, mechanical behavior, surface wettability and protein adsorptivity of these scaffolds were investigated. The results showed that the diameter of the nanofibers in the PGNSs was 230 + 68, 197 + 46, 188 + 38 or 164 + 54 nm when the GO content in the scaffolds was 0, 0.25, 0.5 or 1.0%, respectively. The ATR-Fourier transform infrared spectra, Raman spectra, and X-ray diffraction results revealed the successful introduction of GO into the PVA matrix. Mechanical testing indicated that GO increased the tensile strength while reducing the ductility of the scaffolds. The biological properties of the scaffolds were evaluated by water contact angle measurements, protein adsorption assays, hemolysis ratio testing, cell co-culturing and in vivo skin repair in animal models. The results showed that the GO-modified scaffolds had favorable hydrophilicity and enhanced protein-enrichment ability. No visible hemolysis was observed for any of the scaffolds. Cellular behavior on the scaffolds revealed that the PGNSs were suitable for the growth and adhesion of L929 fibroblasts. Moreover, the PGNS containing a 0.25% GO content was the most suitable scaffold for cell viability and adhesion. In vivo wound repair assessments showed that the wound contraction rate when treated by the PGNS containing a 0.25% GO content exceeded 90% within 9 days, suggesting excellent potential of the PGNS for skin tissue engineering.