The vibrational features of 4-fluorobenzonitrile in the first electronically excited state S-1 and cationic ground state D-0 have been studied by two-color resonance enhanced multiphoton ionization and mass analyzed threshold ionization spectroscopy. Most of observed vibrations in the S-1 and D-0 states are related to in-plane ring deformation and CN bending motions. The band origin of the S-1 <- S-0 transition and adiabatic ionization energy of 4-fluorobenzonitrile are determined to be 36,616 +/- 2 and 78,000 +/- 5 cm(-1), respectively. These data provide insight into the substitution effect of fluorine atom and cyano group on the transition energy.