This study raises a salient point in designing a molecularly modified electrode: besides selecting a highly active molecular complex and developing a heterogenization method, a fundamental understanding of the reaction mechanism and possible solvent effects should be considered. The mechanistic changes in the same reaction for the same modified electrode in a different solvent system are attributed to the electrostatic coupling between the molecule and the surface. The intrinsic redox feature of the molecular compound may not always be detected after immobilization if there are no substrates, despite the minimal effect of structural modifications to enable immobilization. In the present study, the strong electrostatic coupling of the anchored metal complex was the key component that caused a dramatic change in the mechanism. It is important to note that the flexible amide linkage plays an essential role in allowing both solvation and surface adsorption to be possible in a single system. In other words, the performance of a heterogenized system is influenced by multiple factors: the molecular analogue, the linkage enabling immobilization, the solvent, and so on, which poses challenges in this exciting frontier.