Co 2+ doped TiO 2 nanofibers with different doping percentages were successfully synthesized using a nonaqueous sol–gel method. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), x-ray photoelectrons spectroscopy (XPS), FTIR and UV–vis spectroscopy were used to characterize the crystal structures, chemical states, morphologies and photocatalytic properties of Co doped TiO 2 nanofibers. Co 2+ doping was found to affect the phase transformation from anatase to rutile. Grain growth activation energy of 17.575kJ/mol was obtained for the TiO 2 nanofibers. The photocatalytic activities of the pure and doped nanofibers were investigated with degradation of methyl orange (MO) as a model pollutant. The degradation followed the Langmuir–Hinshelwood (L–H) kinetic model with pseudo-first-order apparent rates of 3.2×10 −2 , 5.3×10 −2 , 8.9×10 −2 and 7.1×10 −2 for Co doped nanofibers of R t =0.0, 0.0025, 0.005, 0.01 (where R t is the molar ratio of Co(OAc) 2 to Ti(O i Pr) 4 ). The result showed that Co 2+ doped nanostructure significantly enhanced the photocatalytic degradation of methyl orange under direct sunlight compared to pure TiO 2 . R t =0.005 sample showed best sunlight photocatalytic performance among the above samples which is 2.3 times (after 30min) efficient than that of pure nanostructure.