Phase-pure bismuth oxide (Bi2O3) nanorods with an average diameter of 75 nm were fabricated through a facile hydrothermal method for the first time. The UV-vis spectra suggest that the band gap of Bi2O3 nanorods is of a 0.03 eV red shift than the bulky Bi2O3. PL spectra demonstrate that the Bi2O3 nanorods show strong room temperature luminescence at 440 nm. Under UV-pulsed illumination, the photocurrent density of the Bi2O3 nanorod photoanode increases obviously with the applied potential, indicating potential applications in optoelectronic devices.