Three isostructural polyoxometalate-based metal-organic frameworks (POMOFs) [MII2(btap)2(β-Mo8O26)(H2O)4]·4H2O (M = Co 1, Ni 2, Zn 3) based on octamolybdate and 3,5-bis(1',2',4'-triazol-1'-yl)pyridine (btap) were synthesized via the hydrothermal method. POMOFs 1 and 2 and their thermal derivatives could be utilized as efficient electrocatalysts for the oxygen evolution reaction.