Nanofibrous biocomposite scaffolds of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were prepared by using electrospinning method. The microstructure, crystallinity, and morphology of the scaffolds were characterized through X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The mechanical properties were investigated by tensile testing. Moreover, Mouse Osteoblastic Cells (MC3T3‐E1) attachment and proliferation on the nanofibrous scaffolds were investigated by MTT 3‐(4,5‐dimeth‐ylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide assay, SEM observation and fluorescence staining. XRD and FTIR results verify the presence of GO in the scaffolds. SEM images show the three‐dimensional porous fibrous morphology, and the average diameter of the composite fibers decreases with increasing the content of GO. The mechanical properties of the scaffolds are altered by changing the content of GO as well. The tensile strength and elasticity modulus increase when the content of GO is lower than 1 wt %, but decrease when GO is up to 3 and 5 wt %. MC3T3‐E1 cells attach and grow on the surfaces of the scaffolds, and the adding of GO do not affect the cells' viability. Also, MC3T3‐E1 cells are likely to spread on the PVA/GO composite scaffolds. Above all, these unique features of the PVA/GO nanofibrous scaffolds prepared by electrospinning would open up a wide variety of future applications in bone tissue engineering and drug delivery systems. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013