The invention discloses a copper salt catalyzing system. The copper salt catalyzing system is used for catalyzing esterification reaction to prepare a methyl benzoate compound. The copper salt catalyzing system is composed of a copper salt, an oxidant and an alkali, wherein the mol ratio of the copper salt to the oxidant is 1: 15 to 40; the copper salt is selected from one or a mixture of more than one of 8-hydroxyquinoline copper, cupric acetate monohydrate, copper acetylacetonate, cuprous bromide, anhydrous cupric sulfate, copper fluoride dihydrate and pure copper; and the oxidant is one of tert-butyl hydroperoxide, di-tert-butyl oxide or dicumyl peroxide. The newly developed copper salt catalyzing system for benzyl alcohol esterification reaction greatly reduces the reaction cost, the raw materials are simple and easy to gain, the system is in a wide applicable scope of substrates, the yield is up to 99%, the reaction is carried out in the air atmosphere, the operation is simple, and the chemoselectivity is high; and the copper salt catalyzing system is environmentally friendly, has no three-waste discharge, meets green chemistry requirements, and is also beneficial for industrial application.