Thin films of copper oxides were prepared by reactive magnetron sputtering and structural, morphological, chemical, and electronic properties were analyzed using x-ray diffraction, atomic force microscopy, in situ photoelectron spectroscopy, and electrical resistance measurements. The deposition conditions for preparation of Cu(I)-oxide (Cu2O) are identified. In addition, the interface formation between Cu2O and Sn-doped In2O3 (ITO) was studied by stepwise deposition of Cu2O onto ITO and vice versa. A type II (staggered) band alignment with a valence band offset Delta E-VB = 2.1-2.6 eV depending on interface preparation is observed. The band alignment explains the nonrectifying behavior of p-Cu2O/n-ITO junctions, which have been investigated for thin film solar cells. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3592981]