A novel, simple and efficient approach for photodegrading phenol and p-chlorophenol, based on BixOy, was reported for the first time. Monoclinic Bi2O4 was prepared by the hydrothermal treatment of NaBiO3 center dot 2H(2)O. A series of interesting phase transitions happened and various bismuth oxides (Bi4O7, beta-Bi2O3 and alpha-Bi2O3) were obtained by sintering Bi2O4 at different temperatures. The results demonstrated that the Bi2O4 and Bi4O7 phase had strong abilities towards the oxidative decomposition of phenol and p-chlorophenol and very high rates of TOC removal were observed. The characterization by XRD and XPS revealed that Bi4+ in Bi2O4 and Bi3.5+ in Bi4O7 were reduced to Bi3+ during the reaction process. Singlet oxygen (O-1(2)) was identified as the major reactive species generated by Bi2O4 and Bi4O7 for the photodegradation of p-chlorophenol and phenol. This novel approach could be used as a highly efficient and green technology for treating wastewaters contaminated by high concentrations of phenol and chlorophenols. (C) 2015 Elsevier B.V. All rights reserved.