Methylene diphenyl dicarbamate (MDC) was synthesized from methyl phenyl carbamate (MPC) and trioxane using sulfuric acid (H2SO4) as catalyst. The effects of reaction temperature, reaction time, molar ratio of reactants and the content of catalyst have been studied in details. The results showed that H2SO4 exhibited high catalytic activity with the merits of moderate reaction velocity. Under the conditions of n(MPC)/n(trioxane)=3:1, reaction temperature of 95°C, reaction time of 3.5 h and 30% H2SO4, the conversion of MPC reached 99.0% with the selectivity of MDC 81.6%. Moreover, the H2SO4 catalyst was reused five times without obviously activity decrease. Based on the identification of byproducts, a possible reaction mechanism was proposed.