The structural, compositional, and optical properties of ZnO/MgxZn1-xO m-plane heterostructures are investigated using scanning transmission electron microscopy, laser-assisted atom probe tomography, and micro-photoluminescence. Coupled with electron tomography, atom probe tomography is currently the only technique providing a 3D reconstruction of the position of the atoms of a nanoscale specimen with their chemical nature. The multi-quantum well system investigated exhibits a V-groove grating profile along the a-axis accompanied by the formation of Zn- and Mg-enriched regions corresponding to the edges pointing towards the substrate and towards the upper surface, respectively. The optical signature of these heterostructures has been investigated by performing micro-photoluminescence on atom probe tip specimens. Effective mass calculations based on the 3D microscopy data indicate that the quantum well geometry and barrier composition yield a localization of hole states at the bottom of the V-groove. [ABSTRACT FROM AUTHOR]