Energetics, charge selectivity and interfacial charge transfer kinetics affect the efficiency of solar electric energy conversion and solar photochemical formation of fuels. The research described herein focuses on understanding and controlling the energetics, charge selectivity, and interfacial charge transfer processes in organic photovoltaics, as well as new generation semiconductor-semiconductor and metal-semiconductor heterostructured nanorods (NRs) as photocatalysts. Waveguide and transmission based spectroelectrochemistries, photoemission spectroscopies, and impedance spectroscopy were used to characterize the frontier orbital energies, charge selectivity and interfacial charge transfer kinetics in heterostructured NRs and organic photovoltaics. CdSe NRs tipped with Au nanoparticles and CdSe seeded CdS NRs tipped with Pt nanoparticles were used to study the effect of compositional asymmetry and catalytic sites on band edge energies of NRs. We used UV photoemission spectroscopy (UPS) and waveguide and transmission-based spectroelectrochemistry of NR monolayers/multilayers on conductive substrates to estimate valence/conduction band energies. Potential-modulated attenuated total reflectance (PM-ATR) spectroscopy was utilized to measure the apparent heterogeneous rate constants of reversible electron injection into NR films on indium tin oxide (ITO). We conclude from these measurements that metal tipping, which is designed to enhance the photocatalytic activity of semiconductor NRs, altered band edge energies and enhanced electronic coupling to conductive substrates, in ways that are predicted to influence their efficiency as photoelectrocatalysts. Monolayers of functionalized phosphonic acid ruthenium phthalocyanines (RuPcPA) tethered to ITO as a model organic photovoltaic donor/electrode interface were studied to understand the aggregation and orientation dependent charge transfer kinetics and energetics of these systems. The effect of surface roughness on the orientation of RuPcPA was theoretically modeled and compared to the experimental results. Electrochemical and spectroelectrochemical studies revealed the presence of only monomeric species on ITO. Impedance spectroscopy (IS) and PM-ATR were used to measure charge transfer rate constants. Further, frontier orbital energies of RuPcPA modified ITO were measured using UPS, and the results indicated favorable energetics for hole collection at the RuPcPA/ITO interface for OPV applications. The effect of "UV-light soaking" on the performance of organic photovoltaic devices employing metal oxide (MO) electron selective interlayers (ESL) was addressed using sputtered zinc oxide (ZnO) ESL films. This study provides a coherent methodology for differentiating between the proposed origins of the s-shaped current-voltage (J-V) responses in the literature for organic photovoltaics using MO ESLs. We use IS and UPS to demonstrate that the energetic barrier for charge extraction at the ZnO/active layer interface leads to the observed s-shape response in OPVs using ZnO ESLs. Furthermore, this study provides clear guidelines for minimizing the s-shaped J-V response and the effect of UV light on the performances of OPV devices using ZnO ESLs. We have developed solution electrochemical protocols to characterize nanometer-scale porosity and electronic properties of both solution-deposited and sputtered ZnO thin films used as interlayers for electron-harvesting contacts in inverted organic solar cells on ITO substrates. These electrochemical experiments were performed in order to evaluate the hole-blocking abilities of these ZnO ESLs as well as their effective "pinhole density," thus demonstrating a strong correlation to their OPV performances. These electrochemical experiments can be used to characterize and optimize ESLs rapidly, before OPV device fabrication.