Dual atomic catalysts are specially designed for relay activation of peroxymonosulfate (PMS). Here, a programmable metal-triazolate framework is utilized as a precursor to introduce the bimetallic sites (containing Mn and Co) for the synthesis of contiguous Mn−N and Co−N sites anchored on nitrogen-doped porous carbon polyhedral (MCNC). Excellent decontamination performance with TOF/PMS = 46.3 L² min⁻¹ g⁻² is observed on the MCNC, which is 1.6 and 1.5 times of single Mn and single Co catalysts. Singlet oxygen quantifying, ¹⁸O isotope labeling, and theoretical simulations jointly unravel that MCNC activates PMS through a unique “relay” mode, where one site interacts with the O atom in PMS, and the other expedites producing ¹O₂ via PMS* activation. This work advances the origin activation of PMS and enhances the removal for the refractory pollutants by rational regulation of dual site synergistic catalyst, which deepens the on-demand design of Fenton-like reaction.