Novel luminescent vesicles with enhanced emission were successfully achieved for the first time by an amphiphilic europium complex through its spontaneously self-assembly in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6). The complex was prepared by europium ions coordinated with terpyridine ligands, which were modified with the hydrophilic ethoxy chains. The enhanced absolute quantum yield and prolonged fluorescence lifetime of complex in vesicles were observed because of the effective shielding of the quench effects caused by both solvent and complex concentration. Compared to the aggregates formed in other solvents, the vesicles obtained in [Bmim]PF6 showed the best luminescence intensity with the quantum efficiency (37.74%) and luminescent emission lifetime (1.915 ms) both increased about 10 times more. Furthermore, this europium complex was designed to show unsaturated coordination, which made the vesicle luminescence easily quenched when contacting with water. The fluorescence sensing of water with this vesicle as probe was therefore possible, where several unique properties like high sensitivity, low detection limit (0.05 vol %), visible color change, and fast response had been observed. Such designed systems are expected to provide strategies to develop novel supramolecular aggregates in ionic liquids and offer guidance for luminescence detection with facile and wide applications.