The behavior in the bulk and at interfaces of biphilic ionic liquids in which either the cation or anion possesses moderately long alkyl tails is to a significant degree well understood. Less clear is what happens when both the cation and anion possess tails that are not apolar, such as in the case of ether functionalities. The current article discusses the structural characteristics of C2OC2OC2-mim(+)/C2OC2OC2-OSO3 in the bulk and at the vacuum interface. We find that the vacuum interface affects only the nanometer length scale. This is in contrast to what we have recently found in (J. Phys. Chem. Lett., 2016, 7 (19), 3785-3790) for isoelectronic C[8]-mim(+)/C[8]-OSO3-, where the interface effect is long ranged. Interestingly, ions with the diether tail functionality still favor the tail-outward orientation at the vacuum interface and the bulk phase preserves the alternation between charged networks and tails that is commonly observed for biphilic ionic liquids. However, such alternation is less well-defined and results in a significantly diminished first sharp diffraction peak in the bulk liquid structure function.