The roles of benzoic acid and water on the Michael reaction of pentanal and nitrostyrene catalyzed by diarylprolinol silyl ether are revealed by density functional theory calculations. The calculations demonstrate that the benzoic acid is ready to attack the catalysts and form a hydrogen bond between the hydrogen atom of the COOH of benzoic acid and one of the N atoms of the catalyst. The complex formed from pentanal, catalyst and benzoic acid attacks nitroalkene and forms transition states. Finally, the transition states hydrolyze and the products are formed. The calculations demonstrate that the stereoselectivity is dominated by the steric hindrance of the 2-substituent groups, and the benzoic acid can increase the reaction rate evidently by decreasing the activation energies; however, H₃O⁺ or strong acid may prevent the formation of the transition states between enamines and nitroalkenes. The employed solvent can decrease the activation energies and promote the proton transfer from benzoic acid onto the catalyst 2. The calculated enantiomeric excess values are in good agreement with the experimental results. These calculations also reveal that the role of benzoic acid is dependent on the sophisticated structures of the catalysts and provide a valuable index for the structural design of new catalysts and selection of additives or co-catalysts.