1,2-(methylenedioxy)benzene is synthesized by using catechol, dichloromethane and dimethylsulfoxide with the condition of alkali and normal pressure. Overall yield of the process is 73.4%. Influence of material ratio, concentration, temperature and dosage of catalyst on the reaction is investigated and the optimum condition is obtained. Product is analyzed by infrared spectrum and gas chromatogram. Results show that the product is 1,2-(methylenedioxy)benzene and the content by gravity is 98.6%.