PURPOSE: An apparatus for treating non-degradable water using a complex acid chemical oxidation process with a photo-fenton oxidation process and a method thereof are provided to reduce the used quantity of second valent iron catalysts necessary for the photo-fenton oxidation process or a fenton oxidation process, and to reduce the consumption of hydrogen peroxide. CONSTITUTION: An apparatus for treating non-degradable water using a complex acid chemical oxidation process with a photo-fenton oxidation process includes a waste water storage(10), an electrolyte input device(20), an air supplier(30), a non-membrane cell(40), a UV photoreactor(50), and a water collector(60). The non-membrane cell has a plurality of cathodes(41) and a plurality of anodes(42) alternatively. The apparatus for treating non-degradable water further includes a line mixer(70), a circulation pump(80), a venture mixer(90), a porous diffuser(43), a transfer line(100), a pH neutralization chemical injector(110), and a flocculent settling basing(120).
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