La2CoFeO6 bamboo-like hollow nanofibers photocatalytic material was successfully prepared by electrostatic spinning. La2CoFeO6 nanofibers, which were connected to each other by rhombic La2CoFeO6 nanoparticles, had stable one-dimensional structure and clear bamboo-like hollow structure. The specific surface area of as-prepared inorganic nanofibers reached 98.7 m(2)/g. La2CoFeO6 nanofibets had a high utilization for natural light and its band gap was 1.6 eV. When concentration of methyl orange was 10 mg/L with pH of 2 and the dosage of La2CoFeO6 nanofibers was 1.5 g/L, methyl orange was degraded by La2CoFeO6 nanofibers within 2 h under natural light at 96.9%.