We report the fabrication of quantum wells in ZnO nanowires (NWs) by a crystal phase engineering approach. Basal plane stacking faults (BSFs) in the wurtzite structure can be considered as a minimal segment of zinc blende. Due to the existing band offsets at the wurtzite (WZ)/zinc blende (ZB) material interface, incorporation of a high density of BSFs into ZnO NWs results in type II band alignment. Thus, the BSF structure acts as a quantum well for electrons and a potential barrier for holes in the valence band. We have studied the photoluminescence properties of ZnO NWs containing high concentrations of BSFs in comparison to high-quality ZnO NWs of pure wurtzite structure. It is revealed that BSFs form quantum wells in WZ ZnO nanowires, providing an additional luminescence peak at 3.329 eV at 4 K. The luminescence mechanism is explained as an indirect exciton transition due to the recombination of electrons in the QW conduction band with holes localized near the BSF. The binding energy of electrons is found to be around 100 meV, while the excitons are localized with the binding energy of holes of ∼5 meV, due to the coupling of BSFs, which form QW-like structures.