Y2O3 with particle sizes ranging from 5 nm to 1 μm were studied at high pressure using x-ray diffraction and Raman spectroscopy techniques. Nanometer-sized Y2O3 particles are shown to be more stable than their bulk counterparts, and a grain size-dependent crystalline-amorphous transition was discovered in these materials. High-energy atomic pair distribution function measurements reveal that the amorphization is associated with the breakdown of the long-rang order of the YO6 octahedra, while the nearest-neighbor edge-shared octahedral linkages are preserved.