The invention is a device and method for purifying sulfur dioxide and nitrogen oxide in flue gas with an electrolysis-chemical advanced oxidation enhanced ammonia method. The device includes a thermal activation reactor, ammonium hydroxide storage tank, absorption tower, electrolytic bath and crystallization separator. The method takes raw material part of an ammonium sulfate solution that is a reaction product of ammonia and sulfur oxide in flue gas, and an ammonium persulfate solution prepared by electrolysis of an electrolytic bath as an oxidant to enhance the efficiency of purifying sulfur dioxide and nitrogen oxide in the flue gas with an ammonia method. A thermal activation reactor activates an ammonium persulfate containing solution to generate a strong oxidizing SO4.−, so that NOx and SO2 in the flue gas may be more efficiently converted into a product having higher solubleness for enhanced removal of sulfur dioxide and nitrogen oxide in the flue gas.