•The synergetic effects of GO and PVP on membrane performance were investigated.•The surface hydrophilicity of membrane was enhanced by the synergistic effects.•The anti-fouling performance was obviously improved in PVDF/GO/PVP membrane.•The optimized performance can be obtained at the stipulated GO and PVP contents. Membrane surface and cross-sectional morphology created during membrane formation is one of the most essential factors determining membrane separation performance. However, the complicated interactions between added nanoparticles and additives influencing membrane morphology and performance during building membrane architectures had been generally neglected. In this study, asymmetric PVDF composite ultrafiltration (UF) membranes containing graphene oxides (GO) were prepared by using N-methyl pyrrolidone (NMP) as solvent and polyvinylpyrrodione (PVP) as the pore forming reagent. In the first time, the effects of mutual interactions between GO and PVP on membranes surface compositions, morphology and performance were investigated in detail. The variation in chemical properties of different membranes and hydrogen bonds in the membrane containing GO and PVP were confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR). Atomic force microscopy (AFM), scanning electron microscopy (SEM), and contact angle (CA) were utilized to clarify the synergetic effects of GO and PVP on morphologies and surface hydrophilicity of membranes. Besides, water flux, bovine serum albumin (BSA) rejection and attenuate coefficient were also determined to investigate filtration performance of various membranes. Compared with pure PVDF membrane, the comprehensive performance of PVDF/GO/PVP membrane has been obviously improved. The surface hydrophilicity and anti-fouling performance were enhanced by the synergistic effects of incorporated GO and PVP. When the PVP content was 0.25wt.% and the GO content was 0.5wt.%, the optimized performance can be obtained due to the formation of hydrogen bonds between GO and PVP.