The redox relay that is necessary for water splitting in dye sensitized photoelectrochemical cells (DSPECs) requires a controlled nanostructure at the photoanode/photocathode surface, such that light absorption and exciton dissociation are followed by the movement of charges to a redox activated catalyst. To improve the efficiency of this process, chromophore/catalyst assemblies have been developed in order to control the spatial organization of these critical components at the electrode surface. In this work, we describe two different supramolecular approaches to chromophore/catalyst assemblies using both covalent and non-covalent strategies. For the oxidative photoanodic reaction H2O → H+ + O2, covalently linked chromophore/catalyst assemblies have been synthesized which utilize terthiophene or thiophene-benzothidiazole chromophoric units linked to a ruthenium water oxidation catalyst. The use of organic chromophores instead of the more common ruthenium polypyridyl based chromophores afforded a stronger and broader absorption, resulting in more efficient light harvesting. These covalently linked chromophore/catalyst assemblies were anchored to a metal oxide surface via a phosphonic acid moiety to produce a functional photoanode, which showed enhanced photocurrent compared to a catalyst control. Oxygen formation was monitored via a Unisense probe, demonstrating sustained water splitting in the newly developed assemblies. For the reductive photocathodic reaction H+ → H2, a second project has focused on ionic assemblies utilizing anionic chromophores and a cationic Ni(II) based proton reduction catalyst to construct non-covalent, electrostatic complexes. These ionic chromophore/catalyst assemblies can be deposited as nanostructured thin-films using the layer-by-layer technique, enabling a convenient fabrication approach for DSPECs. We will discuss the synthesis of the new ionic materials and describe their self-assembly behavior along with their optical and redox properties. Layer-by-layer deposition of the assemblies and preliminary characterization of their electrocatalytic behavior will also be addressed.