A method for electrolysis-ozone-corrosion inhibitor/electrolysis-ozone-hydrogen peroxide-corrosion inhibitor coupling treatment on toxic and refractory wastewater includes the following steps: adding toxic and refractory wastewater to be treated into a wastewater treatment reaction tank equipped with a plate anode and a plate cathode, and starting a direct current (DC) power supply connected to the plate anode and the plate cathode to treat the toxic and refractory wastewater at an appropriate current density under stirring, during which a corrosion inhibitor and hydrogen peroxide are added to the toxic and refractory wastewater to be treated and ozone is introduced into the toxic and refractory wastewater to be treated through an aeration device. The method can increase the production rate and production quantity of free radicals in a reaction system, effectively improve the treatment efficiency for toxic and refractory wastewater, and reduce the treatment cost.