Ca-doped TiO₂ nanofibers have been synthesized by sol-gel and electrospinning techniques with calcium acetate as the calcium source and titanium isopropoxide as titanium source. Their structures and morphologies of the samples were analyzed and characterized by XRD and SEM, which reveal TiO₂ nanofibers are mainly composed of the rutile structure with small amounts of anatase phase. Meanwhile, the photocatalytic activity of TiO₂ nanofiber catalyst has been evaluated with the photodegradation reaction of the water-soluble Rhodamine B. The results show that the Ca-doping of the TiO₂ nanofiber can effectively improve its photocatalytic activity for the degradation of the water-soluble Rhodamine B. The degradation percentage of rhodamine B in the solution of 1 × 10_-5 mol / L is about 95% as the Ca-doping concentration = 5at. % (optimum value), the content of TiO₂ in solution = 1.2 × 10_-2 g / L and UV light irradiation time =100 min.