Degradation efficiency and catalyst stability are crucial issues in the control of organic compounds in wastewater by advanced oxidation processes (AOPs). However, it is difficult for catalysts used in AOPs to have both high catalytic activity and high stability. Combined with the excellent activity of cobalt/copper oxides and the good stability of carbon, highly dispersed cobalt-oxide and copper-oxide nanoparticles embedded in carbon-matrix composites (Co-Cu@C) were prepared for the catalytic activation of peroxymonosulfate (PMS). The catalysts exhibited a stable structure and excellent performance for complete phenol degradation (20 mg L−1) within 5 min in the Cu-Co@C-5/PMS system, as well as low metal-ion-leaching rates and great reusability. Moreover, a quenching test and an EPR analysis revealed that ·OH, O2·−, and1O2were generated in the Co-Cu@C/PMS system for phenol degradation. The possible mechanism for the radical and non-radical pathways in the activation of the PMS by the Co-Cu@C was proposed. The present study provides a new strategy with which to construct heterostructures for environmentally friendly and efficient PMS-activation catalysts.