We show that the ability of the ligand to reorganize the electric double layer (EDL) often dominates the electrocatalysis contrary to their inductive effect in the spectrochemical series, leading to counterintuitive electrocatalysis. With water oxidation and chlorine evolution as the probe reactions, the same catalytic entity with carboxy functionalized ligand exhibited surprisingly higher electrochemical activity in comparison to the aggressively electron-withdrawing nitro functionalized ligands, which is contrary to their actual location in the spectrochemical series. Spectroscopic and electrochemical analyses suggest the enrichment of catalytically active species in the carboxy substituted ligand via proton charge assembly in the EDL that in turn enhances the kinetics of the overall electrochemical process. This demonstration of less obvious ligands becoming indispensable in electrocatalysis suggests a blind designing of ligands solely based on their inductive effect should be reconsidered as it will prevent the utilization of the maximum potential of the molecule in electrocatalysis.