Methylene blue simulated wastewater was treated with a UV-H2O2 combined system. Influences of factors such as reaction time, initial pH value and H2O2 dosage were investigated, and the reaction kinetics of the process was explored. Results showed that the degradation of methylene blue happened only in the presence of both conditions: UV irradiation and H2O2 addition. Initial pH and H2O2 dosage had a remarkable influence on the degradation efficiency. Through several groups of univariate experiments, the optimum pH and H2O2 dosage of the photolysis process were found to be 4–5 and 0.165 mL 30% H2O2 per milligram of methylene blue, respectively. The photolysis process was relatively fast at the initial stage and, 20 min later, it was approximately in accordance with the first-order kinetic equation.