In this work, simulations of the electronic band structure of a p-GaN/n-ZnO heterointerface are presented. In contrast to homojunctions, an additional energy barrier due to the type-II band alignment hinders the flow of majority charge carriers in this heterojunction. Spontaneous polarization and piezoelectricity are shown to additionally affect the band structure and the location of the recombination region. Proposed as potential UV-LEDs and laser diodes, p-GaN/n-ZnO heterojunction nanowires were fabricated by plasma-assisted molecular beam epitaxy (PAMBE). Atomic resolution annular bright field scanning transmission electron microscopy (STEM) studies reveal an abrupt and defect-free heterointerface with a polarity inversion from N-polar GaN to Zn-polar ZnO. Photoluminescence measurements show strong excitonic UV emission originating from the ZnO-side of the interface as well as stimulated emission in the case of optical pumping above a threshold of 55 kW/cm(2).