A residue containing vanadium and chromium was precipitated from a wastewater mill. Electro-oxidation technology and H2O2 acting as reinforcement methods were introduced for vanadium leaching from the residue. During the leaching process, sodium hydroxide could provide an appropriate reaction medium and promote the reaction rate of the acidic oxides. Electro-oxidation technology and H2O2 could produce some fresh and nano-/micrometer-size oxygen bubbles, which could oxidize vanadium in low valence to high valence. The kinetics investigation indicated that the leaching process was followed by a surface chemical reaction model, and the leaching efficiency increased along the increase of the temperature and reaction time. The apparent activation energy decreased with the intensification of electro-oxidation technology and H2O2. Electro-oxidation technology coupled with H2O2 exhibited the lowest apparent activation energy as 6.48 kJ mol(-1).