In 1982, the Meyer group reported ruthenium polypyridyl complexes as water-oxidation catalysts (WOCs). To date, many other molecular catalysts have been reported; however, several issues hamper their large-scale utilization, including poor reusability and the solubility of the catalysts, the need for sacrificial oxidants (e.g., ceric ammonium nitrate), and the harsh (acidic or alkaline) reaction conditions. Slow reaction rates, low catalyst stability, and high costs are other limitations. Low potentials are required to drive reactions with high current densities. Among various materials, transition metal oxides of ruthenium, iridium, manganese, cobalt, platinum, and their clusters are widely studied for electrocatalytic water splitting. For example, Negishi, Pal, Xu, Lu, and others reported the use of Pd-Mn3O4 and other catalytically active nanoclusters. In recent years, heterogenized catalysts on conducting surfaces have been shown to be chemically robust and reusable. The optimization of the catalytic process also includes searching for suitable materials that can immobilize and stabilize the clusters. Recently, the use of polyethyleneimine-modified reduced graphene (rGO) was found to support bimetallic gold-palladium nanoparticles for electrocatalysis. Metal-organic frameworks (MOFs) have also been shown to be promising electrocatalysts. MOFs have been dropcasted onto electrodes by use of a perfluorinated polymer containing sulphonic acid groups (Nafion) as a binder. Their high porosity allows the electrolyte and water molecules to access the catalytic sites. Farha and Hupp investigated MOFs based on cobalt formed by atomic layer deposition for electrochemical water oxidation under alkaline reaction conditions. Morris, Ott, and Fischer also reported the use of immobilized MOFs in electrochemical water oxidation. We have developed in our laboratory a series of nanoscale metallo-organic assemblies (MAs) that are redox-active, thermally stable, and highly porous. Coordination-based networks, comprising layers of polypyridyl complexes and metals salts, have been generated on transparent conductive substrates (TCOs) by Layer-by-Layer (LBL) assembly, automated spray-coating, or spin-coating. Whereas the polypyridyl complexes are the functional components, the metals salts (mainly palladium) function as a crosslinker by binding to the pyridyl moieties of polypyridyl complexes, generating 3D networks. The large structural versatility of our MAs has resulted in diverse and potentially useful functions: interlayers for efficient inverted bulkheterojunction solar cells, mimicry of logic gates and circuits (including flip-flops), memory elements, supercapacitors, antibacterial coatings, and directional electron transfer. Furthermore, these materials have excellent charge trapping and multistate electrochromic characteristics. Higuchi, Li, Kurth, Nishihara, Zenkina, Zharnikov, and others have studied related materials in attempting to achieve some of these functionalities. However, the electrocatalytic properties of these MAs have not been explored.