Belonging to the technical field of oxalate ester preparation, the invention aims to provide a catalyst which has high activity and high selectivity and is used in a reaction between carbon monoxide and nitrous acid ester for gas-phase synthesis of oxalate ester as well as its preparation method. The catalyst takes alpha-Al2O3 as a carrier, adopts palladium as a main active component, and employs copper as a first auxiliary agent and M as a second auxiliary agent, wherein, M can be ferrum, nickel, zinc, cobalt, titanium, cerium, molybdenum or tungsten. In terms of the carrier mass, the catalyst is composed of: 0.01-0.5 wt% of palladium, 0.01-1.0 wt% of copper, and 0.01-1.0 wt% of M. Prepared by a deposition-precipitation method, the catalyst of the invention can be used for carbonylation of CO and nitrous acid ester so as to synthesize oxalate ester. And the catalyst is used at a reaction temperature of 80-140DEG C, a reaction pressure of normal pressure to 1.0Mpa, and a reaction space velocity of 500-9000h<-1>. The catalyst provided in the invention has high reaction activity and selectivity, good repeatability of reaction performance, low cost, and simple preparation method, thus being easy for large-scale production.