According to the need of reclamation and utilization of the byproducts crude methyl benzoate in 14 the production of terephthalic acid dimethyl ester by the Witten-Hercules method, the processes of the preparation of benzoic acid esters such as benzyl and butyl benzoate by transesterification of crude methyl benzoate were studied. The processes of the synthesis of benzyl and butyl benzoate were investigated using different technologies including batch rank reaction and reactive distillation. The results show that benzoic acid esters can be obtained particularly easily with high conversions without the formation of additional byproducts, the catalyst titanate has a high activity, and the reaction conversions of the preparation of benzyl and butyl benzoate are respectively up to 100% and 82.79% under the proper conditions.