Photocatalytic reactions to create chemical fuels using semiconductor nanoparticles (NPs) are a promising means of solar energy conversion, provided that the desired photoelectrochemical processes compete successfully with recombination reactions and photocorrosion of the NPs. Our recent strategies have focussed on creation of new electron-rich thiophene-terminated capping ligands for CdSe NPs, and the dark and photoelectrochemical characterization of these new materials as thin films, electrochemically “wired” to a transparent conducting oxide substrate. A hot-injection method was used to obtain CdSe NPs, yielding reasonably monodisperse NPs of 2-5 nm diameter, initially with long-chain alkyl amine capping ligands. Ligand substitution was used to add ligands with electroactive pendant groups, which provide for cross-linking into electrochemically grown, electron-rich conducting polymer films. Dark and photoelectrochemical studies of these thin films, in the presence of solution electron acceptors such as methyl viologen (MV++/MV+.), suggest that some degree of rectification is seen in their electrochemical response with small photovoltages associated with the onset of photocurrent. Luminescence quenching of the NP is also observed beginning at the onset potential for photoelectrochemical response, confirming the donation of electrons in the photoexcited NP, associated with a significant enhancement in the rates of MV++/MV+. electron transfer. This presentation will focus on the formation of these new NP assemblies, the electrochemical cross-linking of these NPs into conducting polymeric matrices, and the photoelectrochemical and photophysical evaluation of their potential for efficient energy conversion and formation of chemical fuels.