We report the vibronic and cation spectra of 2,5-difluoroaniline. The band origin of the S 1 ←S 0 electronic excitation and adiabatic ionization energy are found to be 34451 and 65205cm −1 , respectively. The vibronic bands at 98,220, 290, and 695cm −1 result from the substituent-sensitive bending and those at 445, 535, and 730cm −1 correspondto the in-plane ring deformation vibrations of this molecule in the electronically excited S 1 state. The distinct features at 311, 334, 394, 498, and 738cm −1 in the cation spectra result from the substituent-sensitive bending and in-plane ring vibrations in the D 0 state.