Photoelectrochemical Cells (PECs) show great potential as a highly efficient platform for direct solar power generation. PECs are composed of an organo-metallic photosensitive dye physisorbed onto a metal oxide framework that is attached to the working electrode of an electrochemical cell. Charges that are produced when photons strike the dye molecules must cross several different interfaces before they can be utilized as current carriers. As such, it is easy to understand that improving the mobility of these charges across the dye/metal oxide or metal oxide/electrode interface will directly impact the overall efficiency of a PEC. In this work, we report on preliminary experiments being conducted on the electron transport at the nanoscale in a metal oxide nanowire based PEC by using an electrochemical potentiostat connected to an atomic force microscope to study the topography of the nanowires and the electrochemical behavior of the dye molecule/metal oxide nanowire mat. The influence of the interfacial interactions on electron transfer within the nanowires matrix and the effect of charge transfer from the dye to the nanowires and its effect on the efficiency of the PEC will be discussed. The changes in the electrochemical behavior of the PECs both in the presence and absence of light will be compared to discuss the conditions at which higher photochemical conversion of electrons into electrical energy can be achieved which should result in an overall enhancement of the efficiency within PECs.