Al:HfO2 is grown on III–V compound substrates by atomic layer deposition after an in situ trimethylaluminum-based preconditioning treatment of the III–V surface. After post-deposition rapid thermal annealing at 700 °C, the cubic/tetragonal crystalline phase is stabilized and the chemical composition of the stack is preserved. The observed structural evolution of Al:HfO2 on preconditioned III–V substrates shows that the in-diffusion of semiconductor species from the substrate through the oxide is inhibited. Al-induced stabilization of the Al:HfO2 crystal polymorphs up to 700 °C can be used as a permittivity booster methodology with possibly important implications in the stack scaling issues of high-mobility III–V based logic applications.