A new naphthalene derivative containing a urea group at the 1,8-position of naphthalene was synthesized and showed a unique absorption and fluorescence peak with fluoride ion. Calculations suggested that a new peak was attributed to the increased anionic character of urea nitrogen due to the strongly charged hydrogen bonding between fluoride and amide protons of the urea. The fluoride selectivity among halides (F(-), Cl(-), Br(-)) comes from the fact that the fluoride approaches much closer to the amide protons than other halides and resides in the cavity with fast dynamics. The nature of electronic transitions that were analyzed from the calculations by the collective electronic oscillator method also supports the anionic nature of the complex between host and fluoride.