Formulations involving partially and fully fluorinated media represent a technological challenge given the lipophobic and hydrophobic nature of such liquids. The identification of self-associating materials with which to control the viscosity and solubilizing characteristics of fluorinated solvents is a particularly interesting area of research. It is shown here that the presence of the stereogenic centers inherent in a family of bis-(alpha,beta-dihydroxy ester)s is an essential requirement for the thermoreversible gelation of mixtures of partially fluorinated liquids 2H,3H-perfluoropentane (HPFP) and 1H,1H-heptafluorobutanol (HFB). Gelation is driven by hydrogen bonding, which induces a nonpreferred conformation around the bis-(alpha,beta-dihydroxy ester) structural motif, An analysis of the melting temperature yields an enthalpy of melting that is consistent with three to four hydrogen bonds, commensurate with the end-group structure of the gelator. Small-angle neutron scattering demonstrated the existence of the common fibrillar structures whose dimensions showed no obvious correlation with the molecular structure of the gelator.