Abstract: Polyacrylonitrile (PAN)/titanium dioxide (TiO2)-grapheneoxide (GO) hybrid fiber membranes were prepared by an electrospinning method, followed by calcination. The morphology, crystallization behaviors, thermal properties and photocatalytic performance of the hybrid fibers were investigated by scanning electron microscopy, X-ray diffraction, thermogravimetic analysis and spectrophotometry. The results indicated that tetrabutyltitanate hydrolysateswerewell converted to anatase TiO2 after calcinations. The fiber diameter decreased gradually to a minimum value of 25 nm with an increase of tetrabutyltitanate content.Moreover, the addition of tetrabutyltitanate improved the thermal stability of the fibers. In addition, a methine blue degradation experiment confirmed that the photocatalytic activity of the fibers was improved due to the addition of tetrabutyltitanate. Summarily, the PAN/TiO2-GO hybrid fiber membranes developed by this work can be used as a photocatalyst.