Novel P-O codoped g-C3N4 with large specific surface area is hydrothermal synthesized assisted by dissolution-precipitation process. The XRD, UV-vis, SEM and PL results indicate that the introduction of phosphorus and oxygen enhances the specific surface area of graphitic carbon nitride (from 12.8 to 92.5 m(2) g(-1)), restrains the crystal growth, decreases the band gap energy (from 2.68 to 2.51 eV) and increases the separation efficiency of photogenerated electrons and holes, which increases the anoxic photocatalytic RhB degradation constants by approximately 27 times under visible light. Oxygen doping not only promotes the adsorption ability of reactant but also captures the photogenerated electrons to produce photogenerated holes for RhB degradation under anoxic condition. This study provides new insight into the design and fabrication of oxygen-free photocatalysts. (C) 2015 Elsevier B.V. All rights reserved.