AbstractNanoparticles in solution interact with their surroundings via hydration shells. Although the structure of these shells is used to explain nanoscopic properties, experimental structural insight is still missing. Here we show how to access the hydration shell structures around colloidal nanoparticles in scattering experiments. For this, we synthesize variably functionalized magnetic iron oxide nanoparticle dispersions. Irrespective of the capping agent, we identify three distinct interatomic distances within 2.5 Å from the particle surface which belong to dissociatively and molecularly adsorbed water molecules, based on theoretical predictions. A weaker restructured hydration shell extends up to 15 Å. Our results show that the crystal structure dictates the hydration shell structure. Surprisingly, facets of 7 and 15 nm particles behave like planar surfaces. These findings bridge the large gap between spectroscopic studies on hydrogen bond networks and theoretical advances in solvation science.