Interfacial charge sepn. in hybrid solar cells depends on both the energetic alignment and electronic coupling between the inorg. and org. semiconducting materials at the hetero interface. In the present work, bilayer solar cells comprising the small mol. semiconducting dye TDCV-TPA (tris-(thienylene-vinylene)-triphenylamine) and dense titanium dioxide (TiO2) films were investigated. The internal quantum efficiency and degree of photoluminescence quenching were found to be excitation energy dependent. The mol. interaction and interfacial energy level alignment was investigated using a combination of UV-vis and photoelectron spectroscopy (PES). Stationary and time-dependent d. functional theory calcns. were used to assign and distinguish between different exptl. detd. mol. energy levels (PES) and electronic transitions (UV-vis). Photoelectron spectroscopy results suggest surface induced interactions of TDCV-TPA with TiO2 involving the peripheral CN-groups of the mol. which would imply a favorable electronic coupling for photoinduced interfacial charge transfer. In an energy level diagram distinguishing between the different electronic transitions in the mol., the differences in the thermodn. driving force for electron injection from the excited states were found small. Therefore, it is suggested that the obsd. higher internal quantum efficiency at shorter wavelength can be rationalized by a more favorable driving force for the regeneration of holes created at the hetero interface at higher excitation energy.