Over the past decade, electrocatalysis has been recognized as an accessible, scalable, and sustainable tool to address commonly encountered challenges in energy conversion and chemical synthesis. The rational design of functionalized electrodes bearing a tunable molecular moiety has become increasingly popular in electrocatalysis, hybridizing the fields of heterogeneous electrochemistry and molecular catalysis. In pursuit of potent, selective, and efficient catalysts, organometallic complexes mimicking highly efficient metalloenzymes have been brought under the spotlight for applications in electrochemical transformations. The immobilization of molecular catalysts on an electrode surface may be a solution to bridge the gap between freely dispersed molecular compounds and heterogeneous catalysts in electrochemical systems (Figure ). A molecular catalyst in electrochemistry has been previously defined as either a homogenously dispersed compound in solution or active layers of molecules localized near the electrode surface. The significant distinction between heterogeneous vs. molecular electrocatalysis is that, in the latter case, active sites are well-defined molecules. Given their versatility, relatively easy tunability, and the possibility to understand their working mechanisms, homogenous organometallic complexes were introduced to electrochemical systems to increase accessibility and control reactivity. However, solvent incompatibility, slow diffusion rates, low electron transfer rates, and catalyst degradation remain hurdles on the road towards the optimization of catalytic activity. On the other hand, heterogenous catalysts, where electrodes directly participate in electron transfer reactions, are promising for practical applications due to their robust and recyclable nature. It has been shown that immobilizing molecular catalysts onto an electrically addressable surface may help with solvent incompatibility, in addition to promoting electron transfer, simplifying the separation process of products from the catalyst, and preventing the formation of aggregates. Thus, an immobilized molecular catalyst is expected to be more efficient and recyclable in electrochemical synthesis than its non-immobilized counterpart. The chemically modified electrodes prepared from molecular compounds immobilized onto electrically addressable surface/electrode provide an excellent platform for obtaining potent catalysts for key transformations related to energy generation. This review aims to stimulate ideas and critical thinking on the rational design of chemically modified electrodes. By illustrating the unique chemical reactivity and comparing the catalytic behavior of different hybrid systems when molecular catalysts are attached to an electrode, we strive to provide a systematic view of the field. First, we will offer a technical perspective on the possible approaches to immobilize a molecular catalyst on an electrically addressable surface, mainly focusing on carbon-based electrode materials and including a few examples of metal oxide and metal surfaces. Modifications of the molecular moiety to accommodate the functionalized surface via different linkages will be elaborated next. To provide a clear starting point for those who are new to the field, we also include techniques commonly employed in characterizing the modified surfaces. We then discuss molecular electrocatalysis enabled by anchored catalysts prepared from covalent or non-covalent immobilization of the electrode surfaces. In addition to detailed methods of functionalization, a particular attention is devoted to the electrochemical control and tunability of the functionalized catalysts and their subsequent catalytic performance, especially on reactions related to energy conversion and small molecule activation. Moreover, some compelling examples discussing the effect of external electric fields in a hybrid system on catalytic turnover will be included to showcase the diversity of future applications. As this review will elaborate on the difference and connections between electrocatalysis and catalysis powered by electrostatic interactions, as well as the crucial roles of the molecular attachment involved in both cases, we aim to inspire researchers to interface organometallic chemistry, surface chemistry, and electrochemistry.