A method of recovering vanadium, nickel and molybdenum from heavy crude oil refinery residues comprises pyrolysis and combustion of the residues at temperatures up to 900° C. to produce an ash, converting the ash to an aqueous slurry comprising sodium hydroxide as leading agent and hydrogen peroxide as oxidizer, and extracting vanadium, nickel and molybdenum salts and oxides from the slurry. Extraction processes for the metals are disclosed.