A natural photosensitizer riboflavin (Rf), known as vitamin B-2, and ail environmental friendly strong oxidant hydrogen peroxide (H2O2) were employed for the riboflavin-sensitized photooxidation process (UV/Rf/H2O2) in this study. This approach Could be considered as a hybrid process of UV/Rf (photosensitization) and UV/H2O2 (advanced oxidation). The photodecay of a phenylurea herbicide monuron was investigated by varying the doses of Rf and H2O2 in this work. The use of UV/Rf/H2O2 showed a promising performance for degrading monuron compared with the direct photolysis (UV), UV/Rf, and UV/H2O2 processes. it was found that more than 99% of the monuron was removed in the UV/Rf/H2O2 process in less than 70nnin depending on the dosages of Rf and H2O2. In general, the overall improvement of UV/Rf/H2O2 process Would achieve as high as similar to 450% comparing to sole-UV process. In addition, a kinetic model for the UV/Rf/H2O2 process was developed successfully in this study to facilitate the prediction of the additional performance on the degradation of monuron comparing with the daughter processes (UV, UV/Rf, and UV/H2O2). (C) 2009 Elsevier B.V. All rights reserved.