Organic photovoltaic (OPV) devices offer a promising route to low-cost solar energy harvesting. These systems have demonstrated heterogeneous ultrafast charge transfer dynamics in part due to complex micro and nanoscale disorder at semiconductor domain interfaces. We have investigated the effects of local morphology on interfacial electronic structure using the model system of pentacene grown on Si(111). Spatially resolved two photon photoemission spectroscopy was used to map local variations in interfacial dipole formation and intraband state densities. These results are correlated with film topography as measured by AFM and bulk surface character as measured by conventional UPS. Findings are discussed in the framework of their implications on charge transfer dynamics and successful OPV development.