A GaN/AlxGalxN multi-quantum well test structure with Al concentrations 0 ≤ xAl ≤ 1 was utilized to investigate the growth of AlxGal–xN barrier layers deposited by metal organic chemical vapor deposition (MOCVD). A transition from a two dimensional (2D) to a three dimensional (3D) growth mode was observed in AlxGa1–xN barriers with XAl ≥ 0.75. It is argued that the transition occurs because of growth at temperatures that are low compared with the materials melting points Tmelt. The resulting rough AlxGa1–xN surfaces can be planarized by overgrowth with GaN. Quantitative high resolution electron microscopy (HREM) was applied to measure composition and strain profiles across the GaN/AlxGa1−xN stacks at an atomic level. The measurements reveal a substantial variation of lattice constants at the AlxGa1−xN/GaN interfaces that is attributed to an Al accumulation.