ZnCo-ZIFs was successfully synthesized by a solvothermal method in methanol solvent at room conditions and determined physical–chemical properties by a series of characterization techniques. The catalytic activity of ZnCo-ZIFs on Methyl Blue (MB) degradation in the presence of peroxymonosulfate (PMS) was examined by variation of the effective factors including ZnCo-ZIFs dosage, mass ratio of ZnCo-ZIFs:PMS, temperature, reaction time and initial MB concentration. The result showed that MB was mostly degraded at initial MB concentration of 50 mg L−1 with catalyst dosage of 50 mg L−1 and ZnCo-ZIFs:PMS ratio of 1:3 at room temperature within 20 min of reaction. The main mechanism for dye degradation was the Fenton-like reaction via major active species SO4·‾ (sulfate free radical) generated from PMS by Co2+ metal centers in the catalyst frameworks. The ZnCo-ZIFs showed highly efficient catalytic activity and stability compared to both homogeneous (cobalt salt, zinc salt and 2-methylimidazole) and heterogeneous (ZIF-67, ZIF-8, zeolite ZMS-5 and activated carbon) catalysts. The recyclability of the catalyst also showed an impressive result with 93.6% at the 5th recycle. To the best of our knowledge, ZnCo-ZIFs associated with PMS was first reported as a novel Fenton-like heterogeneous catalyst for MB degradation in water.