Deep eutectic solvents (DESs) are low-melting mixtures, often prepared from a salt and a molecular hydrogen bond donor. Like ionic liquids, DESs that contain at least one sufficiently amphiphilic component can form bicontinuous nanostructures consisting of polar and nonpolar domains, although this has not been widely explored for many DES combinations. Here, the bulk nanostructures of DESs comprising tetraalkylammonium bromide salts (tetrabutylammonium bromide, tetraoctylammonium bromide, and methyltrioctylammonium bromide) with alkanols and alkanoic acids of systematically varied chain lengths (C2, C6, C8, and C10) as hydrogen bond donors have been studied. Small-angle X-ray scattering techniques were used to identify the relationship between the alkyl chain length and functionality of the hydrogen bond donor on the nature of the amphiphilic nanostructures formed. These findings demonstrated that the amphiphilic nanostructures of the DESs were not affected by the functional group on the hydrogen bond donor, with these nanostructures influenced primarily by both the absolute and relative alkyl chain lengths of the salt and hydrogen bond donor.