The reaction kinetic of the synthesis of methacrylic anhydride was investigated with a batch stirred-tank reactor at atmospheric pressure using methacrylic acid and acetic anhydride as raw materials. The reactions were conducted at several temperatures between 343.15 and 363.15 K and at various starting reactant compositions. A homogeneous reversible reaction of the second order was described. A batch reactive distillation column was employed to obtain methacrylic anhydride. The influence of feed molar ratio, reflux ratio, and entrainer on the reaction was investigated, and a suitable operating parameter was obtained. Under these conditions, the conversion of methacrylic acid was 99.95%, and the yield of methacrylic anhydride was 86.99%.