Transparent conductive oxides (TCOs) are important contact materials in thin film solar cells. It is thus important to understand their basic interface properties as the band alignment. We present results on the determination of interfacial properties of TCOs using photoelectron spectroscopy. Large interface dipole potentials are generally observed at interfaces between conducting oxides ZnO, SnO2, In2O3 and TiO2 and chalcogenide semiconductors CdS, CdTe and Cu2S, leading to small conduction band discontinuities in the case of ZnO, SnO2 and In2O3 and to large conduction band discontinuities for TiO2. In addition to the band alignment the Fermi level position at the interface determines the contact properties of TCOs in thin film solar cells.