The formation of lyotropic liquid crystalline (LLC) phases from photocurable amphiphilic small molecules offers an effective strategy for fabricating polymeric materials with well-defined nanostructures. Such self-assembly is primarily driven by phase separation between hydrophilic and hydrophobic segments, with hydrophobic interactions playing a crucial role in the formation of ordered structures. However, conventional amphiphiles typically employ hydrocarbon tails, which require relatively long chain lengths to provide sufficient hydrophobic driving force, thereby limiting the achievable structural miniaturization (typically >3 nm). To overcome this limitation, we designed and synthesized a novel polymerizable ionic amphiphile, EAF8-AC, featuring a fluorocarbon tail with high hydrophobicity and low conformational freedom. The LLC behavior of hydrated EAF8-AC at room temperature was systematically investigated. A concentration phase diagram was established, and the self-assembled structures were characterized using polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS). The evolution of mesophase structures was interpreted based on the critical packing parameter (CPP) theory. Compared to conventional hydrocarbon-based amphiphiles, EAF8-AC enables the formation of more compact ordered structures, demonstrating its potential for constructing high-resolution nanomaterials.