The implementation of sputter-deposited TiO x as an electron transport layer in nonfullerene acceptor-based organic photovoltaics has been shown to significantly increase the long-term stability of devices compared to conventional solutionprocessed ZnO due to a decreased photocatalytic activity of the sputtered TiO x . In this work, we utilize synchrotron-based photoemission and absorption spectroscopies to investigate the interface between the electron transport layer, TiO x prepared by magnetron sputtering, and the nonfullerene acceptor, ITIC, prepared in situ by spray deposition to study the electronic state interplay and defect states at this interface. This is used to unveil the mechanisms behind the decreased photocatalytic activity of the sputter-deposited TiO x and thus also the increased stability of the organic solar cell devices. The results have been compared to similar measurements on anatase TiO x since anatase TiO x is known to have a strong photocatalytic activity. We show that the deposition of ITIC on top of the sputter-deposited TiO x results in an oxidation of Ti 3+ species in the TiO x and leads to the emergence of a new O 1s peak that can be attributed to the oxygen in ITIC. In addition, increasing the thickness of ITIC on TiO x leads to a shift in the O 1s and C 1s core levels toward higher binding energies, which is consistent with electron transfer at the interface. Resonant photoemission at the Ti L-edge shows that oxygen vacancies in sputtered TiO x lie mostly in the surface region, which contrasts the anatase TiO x where an equal distribution between surface and subsurface oxygen vacancies is observed. Furthermore, it is shown that the subsurface oxygen vacancies in sputtered TiO x are strongly reduced after ITIC deposition, which can reduce the photocatalytic activity of the oxide, while the oxygen vacancies in model anatase TiO x are not affected upon ITIC deposition. This difference can explain the inferior photocatalytic activity of the sputter-deposited TiO x and thus also the increased stability of devices with sputter-deposited TiO x used as an electron transport layer.