The realization of transparent electronic and optoelectronic devices requires the use of transparent p-n junctions. In this context, understanding the band alignment at the interface between the p- and n-components represents a fundamental step towards the realization of high performance devices. In this work, the band alignment at the interface between Al-doped ZnO (AZO) and Ni-doped Cr2O3 has been analysed. The formation and evolution of the core levels as the interface progressively forms have been followed by means of x-ray Photoelectron Spectroscopy, x-ray diffraction and x-ray reflectivity. A type two (staggered) band alignment was identified, with the valence band offset and conduction band offset found to be 2.6 eV and 2.5 eV, respectively. The electrical behaviour will be discussed in terms of the position of the bands, the presence of band bending and the expected built-in potential and how these can be engineered in order to achieve the maximum performance for this hetero-structure.