The invention belongs to the field of water treatment, and relates to a method for treating wastewater containing complex-state heavy metals and recovering the heavy metals at a cathode by rotating cathode strengthening and photoelectrocatalytic oxidation. According to the invention, a photoanode with high photocatalytic activity is utilized, under the conditions of light radiation and a bias voltage, a large number of holes and hydroxyl radicals are generated, thus a de-complexation process is quickly performed on metal complexes to promote the release of metal ions, and meanwhile, under driving of the rotating cathode, the concentration of the metal ions in the wastewater changes stepwise, and a high-concentration free-metal solution layer is formed near the cathode to make the metal recovery maximized. The method provided by the invention can high efficiently recover the heavy metals in the form of a metal state without adding additional chemical agents, and has the advantages of low processing costs, no generation of chemical sludge and obvious economic value and environmental significance.