Display omitted •The most efficient route was designed for 3D mesoporous α-Co(OH)2 on Ni foam (NF).•Extraordinary catalytic activity of Co(OH)2/NF for peroxymonosulfate was observed.•The cobalt leaching was alleviated by the macroscopic Co(OH)2/NF.•The readily recyclable monolith catalyst benefits the practical application. Cobalt-based catalysts with high stability and facile recovery for heterogeneous peroxymonosulfate (PMS) activation are still rather sparse and therefore highly desirable. Herein, 3D mesoporous α-Co(OH)2 nanosheets was created on robust nickel foam (NF) via facile electrodeposition approach at 6 mA/cm2 for only 400 s. Almost complete removal of phenol can be achieved within 7 min with a degradation rate of 0.39 min−1, 2 times higher than that with ever-prevalent Co3O4 derived from direct calcination of α-Co(OH)2/NF. This can be attributed to the hydrotalcite-like hexagonal structure of α-Co(OH)2 with large interlayer spacing for enhancing the catalytic performance. The low activation energy of Co(OH)2/NF (53.8 kJ/mol) indicates its lower reaction energy barrier for PMS activation. Moreover, the influences of electrodeposition parameters (i.e. current density, deposition time), PMS dosage, initial pH and coexisting anions (HCO3−, SO42−, Cl−) on the phenol degradation were systematically evaluated. The recycling tests revealed the prominent stability of Co(OH)2/NF. The quenching tests verified that SO4− radicals acted as the predominant reactive species for phenol decomposition. The possible reaction mechanisms were proposed based on the intermediates identification. The findings of this work suggest the great potentials of the 3D macroscopic Co(OH)2/NF in water purification, and open up new avenues for scalable preparing recyclable heterogeneous catalysts.