Metal-organic frameworks (MOFs) derived materials have been demonstrated to be promising alternatives for wastewater treatment. In this study, carbon supporting CuCo nanospheres (CuCo@C) with highly exposed active sites derived from bimetallic CuCo-MOF-74 presented excellent stability with continuous five cyclic reaction. The CuCo@C exhibited a highly efficient catalytic performance towards peroxymonosulfate (PMS), resulting in 100% of Orange G (OG) removal in the presence of 2 mM of PMS and extremely low CuCo@C loading of 50.0 mg/L in 15 min. The synergistic effects between Cu and Co and the fast regeneration of low-valence metals were responsible for the excellent heterogeneous catalytic process, where ¹O₂ was generated as the dominant species with some ·OH, and SO₄^•−. Besides, the carbon shell played a vital role in the improvement of CuCo@C stability. The high Fukui nucleophilic (f⁻) index and quantitative structure-activity relationship (QSAR) indicated the preferred attacking sites and toxicity reducing of OG, respectively. The main intermediate products of OG were detected and the possible degradation pathway was proposed. Moreover, CuCo@C/PMS system exhibited broad applicability and compatibility suitable for degradation of various kinds of organic pollutant. The excellent catalytic performance, reduced toxicity of OG intermediates, good stability and reusability of CuCo@C all suggested the great application potential in practical water treatment.