Fluorescence excitation, multiphoton ionization, and dispersed fluorescence spectra of bare and hydrogen-bonded 2-fluoropyridine with water were measured in a supersonic free jet. For bare 2-fluoropyridine, fluorescence quantum yield decrease in the higher vibronic levels was observed even under collision-free conditions. The intersystem crossing channel was probed experimentally by two color R2PI and found to be negligible. The nonradiative relaxation process of 2-fluoropyridine is mainly governed by the relaxation to the electronic ground state. Electronic spectra of 2-fluoropyridine-(water)(n) (n = 1 similar to 3) were also obtained. The hydrogen bond formation with water increases the quantum yield in the higher vibronic levels. Rather low frequency vibrations were observed in the hole burning spectrum of bare 2-fluoropyridine; however, these vibronic bands disappeared with the hydrogen bond formation with water. The appearance of low frequency vibronic bands observed for bare 2-fluoropyridine is ascribed to the existence of closely lying ( n, pi*) state.