The electronic structure and chemical composition of efficient CH₃NH₃PbI₃ perovskite solar cell materials deposited onto mesoporous TiO₂ were studied using photoelectron spectroscopy with hard X-rays. With this technique, it is possible to directly measure the occupied energy levels of the perovskite as well as the TiO₂ buried beneath and thereby determine the energy level matching of the interface. The measurements of the valence levels were in good agreement with simulated density of states, and the investigation gives information on the character of the valence levels. We also show that two different deposition techniques give results indicating similar electronic structures.