In this study, in order to achieve efficient activation of persulfate, we added MoS₂ as a co-catalyst to the iron, cobalt and nitrogen modified biochar (Fe–Co–N–BC) catalytic system. Analytical methods such as scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) demonstrated that the MoS₂/Co–Fe–N–BC catalytic materials were successfully prepared. In the MoS₂/Fe–Co–N–BC/PMS system, 97.5% of PFOA was removed within 180 min with K_obs of 0.074 min⁻¹. Composites with different mass ratios of MoS₂ and Co–Fe–N–BC/PMS in the non-homogeneous PMS system both exhibit excellent catalytic efficiency for TOC removal. In particular, MoS₂/Fe–Co–N–BC obtained extraordinary catalytic efficiency through synergistic radical (SO₄˙⁻, ˙OH) and non-radical (¹O₂, Fe^IV and Fe^V) processes, which was proved by the quenching experiments and the EPR testing. The analysis of the activation mechanism reveals that the three redox ion pairs Fe²⁺/Fe³⁺, Co²⁺/Co³⁺ and Mo⁴⁺/Mo⁶⁺ simultaneously participated in the activation of PMS, realizing multi-path electron transfer. And MoS₂ played an excellent co-catalysis role in promoting the cycling of the valence states of the ions. Compared to Fe³⁺ and Co³⁺, the low valence states of Fe²⁺ and Co²⁺ can activate PMS more rapidly and produce more ˙OH and SO₄˙⁻. However, the recycling efficiency of Fe²⁺ and Co³⁺ in the Fe–Co–N–BC system is low, and the presence of MoS₂ improves the efficiency of Fe³⁺ and Co³⁺ reduction to Fe²⁺ and Co²⁺, respectively. The possible degradation pathways of PFOA were proposed. This study provides some references for the design of polymetallic-doped catalysts to degrade difficult-to-degrade organic pollutants.