In hybrid photovoltaic (PV) devices organic and inorganic materials are combined in absorber thin films contacted by charge selective electrodes. Among others, the major points of combining organic and inorganic materials relate to (i) complementation of the spectral range and (ii) beneficial effect of carrier multiplication in quantum dots (QDs) dispersed in organic semiconductor matrices. When designing hybrid solar cells, it is of importance to consider the excitonic nature of the materials used, e.g. organic small molecules (C60, ZnPc, MgPc, SubPc and ZnPc:C60) and PbSQDs. This is especially essential for organic materials which usually show high exciton binding energies. It is therefore the purpose of this work to study the effectiveness of charge separation at interfaces between excitonic semiconductors and component materials used in hybrid PV devices which are usually conventional semiconductors. The component materials relate to transparent conductive oxides (TCOs), e.g. ITO, ZnO:Al and TiO2 used as transparent electrodes, to Na-free or Na-treated chalcopyrite absorbers, e.g. CuInSe2, and transition metal oxide MoO3 thin films used as buffer layers. The morphology and electronics as well as charge separation and transfer at interfaces between excitonic and conventional semiconductor thin films of hybrid PV devices were investigated by Kelvin Probe Force Microscopy in ultra-high vacuum and surface photovoltage measurements. The investigations were performed for revealing the most appropriate combination of excitonic and conventional materials for most effective dissociation of excitons and charge transfer at respective interfaces. Energetic models are proposed and discussed.