In the quest to rationally design novel mesophase systems the challenge remains to deconvolute the relationship between structure, composition, and function. In the current study, novel glycerol-derived surfactants with high negative interfacial areas and a preference for inverse phase behavior have been targeted and synthesized. This has been achieved by application of the rule-of-thumb afforded by the critical packing parameter (CPP), namely, that inverse phase behavior is favored by wedge-shaped molecules with relatively small head group versus chain volume. Highly splayed hydrophobes with exaggerated cross section such as oleyl (cis-octadec-9-enyl) hexahydrofarnesyl (3,7,11-trimethyl-dodecyl) and phytanyl (3,7,11,15-tetramethyl-hexadecyl) were particularly successful for this purpose across many variations of head group. The phase behavior of the binary system in water of many of these surfactants is relatively simple. Typically, cubic or inverse hexagonal phases exist at the interface with water with the inverse micellar phases present at lower hydration. The inverse liquid crystalline phases were present for a broad range of temperatures and compositions.