The invention relates to a treatment process of copper-iron-contained high-concentration acidic mine wastewater. The treatment process comprises the following sequential process steps: (1) neutralization to remove iron; (2) solid-liquid separation; (3) biological sulfuration; (4) solid-liquid separation; and (5) biological purification for recovering valuable constituents in the wastewater and enabling yielding water to achieve an emission standard. The invention has the advantages of high removal rate of copper, iron and sulfate radicals, strong suitability, low treatment cost, environmental protection, good comprehensive recovery utilization effect, and the like and is particularly suitable for treating the copper-iron-contained high-concentration acidic mine wastewater generated in the copper-extracting production process by a biological wet method and in the mining process of copper sulphide.