Herein, we, for the first time, report a high spin Co-Fe Prussian blue analogue (Co-Fe PBA) as a highly efficient Fenton-like catalyst for sulfate radical (SO4˙-) production. Our experiments and density functional theory (DFT) calculations show that the largely elongated SO4-OH bond length, strengthened adsorption and facilitated electron transfer for peroxymonosulfate (PMS) activation catalyzed by high-spin (HS) CoII are the main factors contributing to its excellent activity.