The catalytic performance of oxalate-based Ni-Fe metal-organic frameworks (MOFs) in the oxygen evolution reaction (OER) was investigated via a coordination strategy. The bidentate chelating ligand 2,2'-bpy (2,2'-bipyridine), was utilized to improve the catalytic kinetics under ambient conditions. The results revealed that a MOF-to-MOF transformation including the formation of [M(2,2'-bpy)n]2/3+ (M = Ni/Fe, n = 1-3) could boost alkaline OER, giving an impressive ultralow overpotential of 220 mV at a current density of 10 mA/cm2 in a 1 M KOH solution, surpassing the performance of control group activity of oxalate-based Ni-Fe MOF. However, excessive addition of the ligand had a negative effect, leading to decreased activity. Further investigation revealed the double role of 2,2'-bpy: Both promote and suppress catalytic reactions. The catalytic mechanism was then discussed, highlighting the potential of secondary ligands to effectively fine-tune the catalytic behavior of these materials.