The size-dependent phase stability of γ-Al 2 O 3 was studied by largescale molecular dynamics simulations over a wide temperature range from 300 to 900 K. For the γ-Al 2 O 3 crystal, a bulk transformation to α-Al 2 O 3 by an FCC-to-HCP transition of the O sublattice is still kinetically hindered at 900 K. However, local distortions of the FCC O-sublattice by the formation of quasi-octahedral Al local coordination spheres become thermally activated, as driven by the partial covalency of the Al−O bond. On the contrary, spherical γ-Al 2 O 3 nanoparticles (NPs) (with sizes of 6 and 10 nm) undergo a crystalline-to-amorphous transformation at 900 K, which starts at the reconstructed surface and propagates into the core through collective displacements of anions and cations, resulting in the formation of 7-and 8fold local coordination spheres of Al. In parallel, the reconstructed Al-enriched surface is separated from the stoichiometric core by a diffuse Al-depleted transition region. This compositional heterogeneity creates an imbalance of charges inside the NP, which induces a net attractive Coulombic force that is strong enough to reverse the initial stress state in the NP core from compressive to tensile. These findings disclose the delicate interplay between lattice distortions, stresses, and space-charge regions in oxide nanosystems. A fundamental explanation for the reported expansion of metaloxide NPs with decreasing size is provided, which has significant implications for, e.g., heterogeneous catalysis, NP sintering, and additive manufacturing of NP-reinforced metal matrix composites.