Heterogeneous electro-Fenton process is widely recognized as intensive in-situ strategy with environmental compatibility. However, the simultaneous elevation of H2O2 production and exploitation efficiency during electrocatalysis remains a challenge. Here, we propose an innovative dual-site catalyst (MoxCo9−xS8−yNy; MCN) with Mo active motifs for enhanced two-electron oxygen reduction reaction and Co active motifs for enhanced reactive oxygen species generation to promote H2O2 generation and fluoxetine (FLX) degradation. As determined by Mo scaling and application performance, the optimal MCN catalyst provided at least 20 % increase in contaminant elimination within 30 min, reduced the reaction potential by over 1.4 eV, and diminished environmental exposure to toxic products. The optimal MCN@CF cathode efficiently removed approximately 96.7 % FLX and 55.1 % total organic carbon at a pH of 3 within 35 min. The critical dual-motif bridge Co–S–Mo mediated by S could disrupt the synergistic *O and *OOH binding energies, significantly penetrating the catalysis barriers. This work unravels the structural optimization evolution of non-single-site catalysts, providing new solutions to the refractory issues of wastewater decontamination