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 S₁ and cationic ground state D₀ vibrational 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 S₁ and D₀ state 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⁻¹ and 78,650 ± 5 cm⁻¹ for 2-fluorobenzonitrile and 35,989 ± 2 cm⁻¹ and 78,873 ± 5 cm⁻¹ for 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 ← S₀ and D₀ ← S₁ were performed based on the above DFT calculations. The theoretical and experimental results were in good agreement. The observed vibrational features in S₁ and D₀ states were assigned according to the simulated spectra and the comparison with structurally similar molecules. Several experimental findings and molecular features were discussed in detail.