Fluorinated organic compounds have superior physicochemical properties than general organic compounds due to the strong C-F single bond; they are widely used in medicine, biology, pesticides, and materials science. In order to gain a deeper understanding of the physicochemical properties of fluorinated organic compounds, fluorinated aromatic compounds have been investigated by various spectroscopic techniques. 2-fluorobenzonitrile and 3-fluorobenzonitrile are important fine chemical intermediates and their excited state S1and cationic ground state D0vibrational features remain unknown. In this paper, we used two-color resonance two photon ionization (2-color REMPI) and mass analyzed threshold ionization (MATI) spectroscopy to study S1and D0state vibrational features of 2-fluorobenzonitrile and 3-fluorobenzonitrile. The precise excitation energy (band origin) and adiabatic ionization energy were determined to be 36,028 ± 2 cm−1and 78,650 ± 5 cm−1for 2-fluorobenzonitrile and 35,989 ± 2 cm−1and 78,873 ± 5 cm−1for 3-fluorobenzonitrile, respectively. The density functional theory (DFT) at the levels of RB3LYP/aug-cc-pvtz, TD-B3LYP/aug-cc-pvtz, and UB3LYP/aug-cc-pvtz were used to calculate the stable structures and vibrational frequencies for the ground state S0, excited state S1, and cationic ground state D0, respectively. Franck–Condon spectral simulations for transitions of S1← S0and D0← S1were performed based on the above DFT calculations. The theoretical and experimental results were in good agreement. The observed vibrational features in S1and D0states were assigned according to the simulated spectra and the comparison with structurally similar molecules. Several experimental findings and molecular features were discussed in detail.