The mass-analyzed threshold ionization spectra of jet-cooled cis- and trans-3-fluoro-N-methylaniline (3FNMA) were recorded by ionizing via the vibrationless 00 and various vibrational levels of the S1 state. The adiabatic ionization energies of cis- and trans-3FNMA are determined to be 61 742 +/- 5 and 61 602 +/- 5 cm(-1), respectively. In the 0-1800 cm(-1) region, most of the observed vibrations in the D0 state result from the in-plane ring deformation and substituent-sensitive modes. For the high-frequency vibration region, the infrared-ultraviolet double-resonance and autoionization-detected infrared spectroscopies were applied to investigate the N-H and C-H stretching vibrations of bare 3FNMA in the S0 and D0 states. The C-H stretching vibrational information, which we failed to obtain for the bare 3FNMA cation, is complemented by recording the infrared-photodissociation spectra of its Ar cluster cation. It is revealed that a red-shifted frequency and an enhanced intensity are observed for the N-H stretch, while blue-shifted frequencies and greatly decreased intensities are found for both aromatic and the methyl C-H stretches. The blue shift of the C-H stretches is first explained by the balance of two factors, namely, the hyperconjugative interaction and the rehybridization effect. Analysis of the vibrational frequencies reveals a correlation between the relative stability of two rotamers in different electronic states and the relative rigidity of aromatic ring, indicating a mechanism of the long-range interactions through bond between the substituents. The density functional theory calculations can well reproduce the vibrational spectra in both S-0 and D-0 states. With the experimental and theoretical data, the substitution and conformation effects on the properties of 3FNMA in the S-0 and D-0 states, including the molecular structures, the reactive sites of electrophilic attack, and the vibrational behaviors, were discussed in detail.