A recovery method of spend catalyst residue hydrofinished by a high-pressure hydroxyl synthesis method comprises the following steps: letting the hydrofinished spend catalyst react with a sulfuric acid dilute solution at the pure mass ratio of 1:3.95-4.58 in a corrosion resistant reactor to generate a mixed solution of nickel sulfate and aluminum sulfate, simultaneously discharging hydrogen, collecting hydrogen for hydrogenation, and filtering to obtain a clarified mixed solution of nickel sulfate and aluminum sulfate; sending the clarified mixed solution of nickel sulfate and aluminum sulfateinto a reduced pressure distiller for reduced pressure distillation, discharging when distilling to reach a saturated solution and cooling in a cooler for crystallization, firstly precipitating out aluminum sulfate nonahydrate according to different melting points of the two substances, then precipitating out nickel sulfate hexahydrate, washing, heating, removing crystal water, crushing, and packaging to respectively obtain basic nickel sulfate and basic aluminum sulfate crystal products. The spend catalyst is used as the raw material for the preparation of basic nickel sulfate and basic aluminum sulfate, thus changing wastes into valuable things. The recovery method creates considerable economic benefit for enterprises.