The invention discloses a high-activity antimony/ titanium composite catalyst, which contains the following components: 1 antimony catalysts, 2 titanium catalysts, 3 first catalyst promoters and 4 second catalyst promoters, wherein the antimony catalysts are oxides and salts of antimony, the titanium catalysts are titanates, the first catalyst promoters are phosphoric acids, phosphorous acids and alkyl groups and/or polyaryl ethers of the phosphorous acids, and the second catalyst promoters are benzothiodiazoles. The antimony/ titanium composite catalyst can be used in a method for preparing polyethylene glycol terephthalate (PET) copolyesters, which includes the following steps: 1 mixing and adding the antimony/ titanium catalyst, the first catalyst promoters, the second catalyst promoters and binary acids into a reaction system, 2 leading the terephthalic acids, esters of the terephthalic acids and excess ethylene glycol to together perform an esterification reaction at temperature of 240-260 DEG C, at pressure of 0.2-0.4MPa and with reaction time of 1-2 hours, and 3 adding copolymerization glycol monomers for a polycondensation reaction to obtain the copolyesters. The antimony/ titanium composite catalyst and the application thereof in the method for preparing the PET copolyesters have the advantages that the catalyst can activate the antimony series catalyst and shortens polycondensation time, and the problem of decreasing of polyester heat stability due to the fact that the antimony series catalyst is apt to yellow products is solved.