This work highlights the electrochromic performance of metallo-organic films in an aqueous electrolyte without sacrificing switching stability and optical properties, compared with organic electrolytes. These findings can eliminate the use of volatile organics in sol-gel devices, and can serve as a new means to apply non-toxic chemicals in electrochromics and electronic devices based on metallo-organic films. Moreover, we have demonstrated that these films have orthogonal properties. Water can be split under mild (neutral) conditions by applying different potentials; this indicates that such materials are also promising for electrocatalysis. Mechanistically, the anodization process is consistent with the formation of nanosized particles that have been observed experimentally. Their exact structure is unknown; however, we expect the formation of palladium oxides under the applied oxidative conditions in water. We obtained evidence for the formation of such nanoparticles, and it was indicated that the water is split by these particles. Another interesting observation is the correlation between the catalytic performance and the number of deposited layers for both molecular assemblies. Although several factors most likely contribute to this effect, we noted that these structurally different assemblies have indistinguishable surface textures. It is most likely that the assembly-water interface plays a dominant role, which has been established for many heterogeneous catalysis applications. Importantly, this study shows that the performance of our MAs is comparable to that of MOFs on a surface. Interestingly, many other metal-organic assemblies reported by us and others could be used for water splitting studies as well.