A novel macrocyclic amphiphile based on hybrid[4]arene containing tri(ethylene glycol) chains as the hydrophilic part and benzene rings as the hydrophobic part was synthesized. It self-assembled to produce nanoparticles and showed lower critical solution temperature behavior that was affected by its concentration and K+. Moreover, amphiphilic H can encapsulate dye G to form host-guest complexes H⊃G, accompanied by significant fluorescence enhancement. H⊃G can further self-assemble to form fluorescent nanoparticles that can be applied in cell imaging.