Abstract The advanced oxidation process based on peroxymonosulfate (PMS) is a new water purification strategy. In this work, Ni/Fe bimetallic atom cluster composite catalyst is prepared by a hydrothermal synthesis to stimulate PMS to produce high concentration singlet oxygen ( 1 O 2 ) and efficiently remove bisphenol A (BPA) from aqueous solution. The experimental data show that in a broad pH range (pH=3–11), the removal rate of BPA by the non‐free radical pathway induced by 1 O 2 is close to 100 %, and the catalyst still has high stability after 5 cycles. The mechanism of BPA removal in NiFe−BC/PMS/BPA catalytic degradation system is investigated by quenching experiment. It is found that 1 O 2 in the system is the most important active component in the degradation process of BPA, and a high concentration of 1 O 2 could promote the rapid degradation of BPA in solution. In this paper, the high catalytic activity and selectivity of bimetallic atomic cluster catalysts can provide new insights for the treatment of phenolic wastewater.