Abstract: To enhance the photocatalysis and recycling abilities of catalyst simultaneously, polyacrylonitrile (PAN) and tetrabutyltitanate (TBT) were used as carbon-nanofibers (CNFs) and TiO₂ precursors, and TiO₂/CNFs composite materials were successfully prepared via electrospinning and heat treatment, and its morphology, crystal structure, optical performance and photocatalytic properties were studied by SEM, XRD, Raman, UV-vis Spectrophotometer and so on. The results show that the crimp shape of the composite material gradually disappears during heat treatment, and TBT is completely transformed into anatase TiO₂ during carbonization with the increase of TBT content. The absorption edge of TiO₂/CNFs composite material is extended from the ultraviolet region of pure TiO₂ to visible, which can improve the utilization of sunlight. At the same time, after simulated solar irradiation for 180 min, the maximum photocatalytic degradation rate of RhB by TiO₂/CNFs composite material reaches 95.71%. Moreover, the photocatalytic degradation efficiency can still reach about 90% after repeated useage for 5 times.