Spent residuum hydroprocessing (RHDP) catalysts are hazardous waste bearing high-content vanadium and large amounts of oily pollutants. In this paper, a process featuring a Fenton-like reaction and alkaline leaching was proposed to recover vanadium from spent RHDP catalysts. In the first step, a Fenton-like reaction using peroxide was conducted to degrade the oily pollutants and make the surface of the spent catalyst becomes hydrophilic. In the second step, the vanadium-containing deposit on the catalyst was leached with 0.5 M Na2S2O8 at 70 °C for transforming vanadium sulfide to oxide in 5 h. In the last step, alkaline leaching was employed to dissolve vanadium from the oxidizing residue at 80 °C for 1 h. It was found that the accumulated leaching efficiency of vanadium can reach up to 90.92%, and only a small part of aluminum and sulfur was dissolved. These results indicated that this combined process can extract vanadium selectively from spent residuum hydroprocessing catalysts under a relatively mild condition.