The invention discloses a PCB copper-containing wastewater treatment method with autocatalytic oxidation as a core. According to the method, acid copper-containing wastewater is used for regulating pH of alkali copper complex wastewater to be nearly neutral or neutral, zero-valent iron is used for reducing copper ion part in wastewater into new elemental copper which is beneficial for following Fenton reaction, under concerted catalysis action of divalent iron and new elemental copper, high-efficiency Fenton reaction is realized under neutral condition so as to break complex, and then, zero-valent iron is used for reduction to recycle copper ions in wastewater, divalent iron and ferric ions in effluent are removed by an alkali regulation precipitation method, meanwhile, under the effects of flocculation and adsorption of ferric hydroxides, pollutants in water are further removed, copper ion concentration is less than 0.5mg / L and iron ion concentration is less than 10mg / L in final effluent, and biodegradability is good. The method fully uses the copper existing in the system and makes use of catalytic effect of copper while removing the copper, dosage of acid and alkali is remarkably reduced, and salt content of effluent is reduced, and the method has an industrial application value.