The invention belongs to the technical field of chemical catalysts and in particular relates to a cerium, rhenium and phosphorus modified electrolytic silver catalyst as well as a preparation method and application of the cerium, rhenium and phosphorus modified electrolytic silver catalyst. According to the cerium, rhenium and phosphorus modified electrolytic silver catalyst, carrier silver adopts electrolytic silver prepared by an electrolytic process; after the silver is subjected to heat treatment of water steam, crystal face reconstruction occurs to the electrolytic silver and the rough surface becomes smooth; the treated electrolytic silver is immersed and loaded with cerium, rhenium and phosphorus compounds and then is roasted after being dried; then the silver is subjected to heat treatment by the water steam again to prepare the cerium, rhenium and phosphorus modified electrolytic silver catalyst. The cerium, rhenium and phosphorus modified electrolytic silver catalyst can be used for carrying out catalytic oxidation on fatty alcohol or aromatic alcohol to generate corresponding aldehyde or ketone in one step; compared with the electrolytic silver catalyst applied in the current industry, the cerium, rhenium and phosphorus modified electrolytic silver catalyst has a very good iron poisoning resisting property.