The nanostructure of a series of choline chloride/urea/water deep eutectic solvent mixtures was characterized across a wide hydration range by neutron total scattering and empirical potential structure refinement (EPSR). As the structure is significantly altered, even at low hydration levels, reporting the DES water content is important. However, the DES nanostructure is retained to a remarkably high level of water (ca. 42 wt % H2 O) because of solvophobic sequestration of water into nanostructured domains around cholinium cations. At 51 wt %/83 mol % H2 O, this segregation becomes unfavorable, and the DES structure is disrupted; instead, water-water and DES-water interactions dominate. At and above this hydration level, the DES-water mixture is best described as an aqueous solution of DES components.