Supramolecular chemistry has asserted itself as a significant multidisciplinary field concerned with molecular effects afforded through non-covalent molecular interactions. The increased interest in the literature towards nanoscale devices, through modulation of molecular function, has seen the renaissance of supramolecular chemistry as function progresses from solution to surface. Heterosupramolecular chemistry follows the architectural principles of supramolecular chemistry and embraces both covalent and non-covalent interactions of condensed phase surfaces and molecular components. A modular approach to device architecture was applied as a novel method of performing photocatalysis under visible light illumination. The application of heterosupramolecular assembly to the design of photoelectrochemical cells capable of visible light induced charge separation allowed the study of interfacial processes by means of electrochemical observations. Preparation of a series of supramolecular components was undertaken as specific molecular species within a photochemical system. Starting from a synthesised bidentate ligand that incorporated an acidic functional group, 4,4'-bis(methyl)phosphonate-2,2'-bipyridine (dmpbpy) as its ethyl ester, was chelated to give the surface sensitisers, bis-(2,2'-bipyridine)-(4,4'-bis(methyl)phosphonato-2,2'-bipyridine)ruthenium(II) dichloride ([Ru(bpy)2(dmpbpy)]Cl2) and cis-bis-(4,4'-bis-(methyl)phosphonato-2,2'-bipyridine)(2,2'-bipyridine)ruthenium(II) dichloride ([Ru(dmpbpy)2(bpy)]Cl2). An electron relay moiety with an acidic functional group, 1-ethyl-1'-(2-phosphonoethyl)-4,4'-bipyridinium dichloride (EVP), was also prepared using a procedure developed by the candidate. The electronic properties of the prepared photosensitisers were examined by theoretical quantum chemical TD-DFT calculations on the molecular structures and singlet excitations were discussed in relation to experimental data. This identified that the lowest lying LUMO states were consistently occupied by 2,2'-bipyridine (bpy) and this was speculated to be a factor affecting quantum injection yields. The effect of microwave modification of colloidal TiO2 suspensions under extended periods of treatment was investigated. Nanoparticles of TiO2 were compared and contrast to similar convection hydrothermally treated TiO2 and a commercial titania product, namely Degussa P25, both of which are utilised in device fabrication. The investigation identified that extended periods of microwave hydrothermal treatment do not greatly enhance the crystallinity and primary grain size of TiO2. The heterosupramolecular assembly of a multi-component photochemical system was constructed from prepared molecular and condensed phase components. It was demonstrated that this device was capable of inducing a photochemical reaction in H2O under irradiation with  > 420 nm in the absence of an organic electron donor. Interpretation of the photocurrents obtained from this assembly provided understanding of photochemical reactions under low light intensities. Optimised conditions for the photochemical reaction was determined to be pH = 5 and illumination yielded = 0.0036% with an apparent quantum yield (AQY) = 1.6%. Photocatalytic decomposition of organic compounds in a dye-sensitised photoelectrocatalytic cell was investigated for the complete mineralisation of EDTA into CO2, H2 and simple amines and interpreted through photocurrent observations. This was extended to a broad range of organic compounds of various solution concentrations as a simulated industrial waste stream. Photooxidation gave unique photocurrent-time profiles which identified two distinct interfacial processes by mathematical treatment of photocurrent transients with a kinetic model. Kinetic parameters were proposed as a factor for qualitative discrimination of the organic compounds. The implications of these results for heterogeneous catalysis were discussed and the formation of Host-Guest complexes as a method of molecular sensing and as specific photocatalytic receptors was proposed.