We report the vibronic and cation spectra of p-vinylaniline, which are recorded by using the resonant two-photon ionization and the mass-analyzed threshold ionization spectroscopic techniques. The band origin of the S 1 ←S 0 electronic transition appears at 31,490±2cm −1 and the adiabatic ionization energy is determined to be 59,203±5cm −1 . Due to the nature of the substituent, the amino and vinyl groups lead to lower electronic excitation and ionization energies by a few thousand wave numbers. Most of the observed active modes result from the in-plane ring deformation and substituent-sensitive vibrations of this molecule in the electronically excited S 1 and cationic ground D 0 states. By comparing the frequencies of the observed active vibrations, one may conclude that the molecular geometry and the vibrational coordinates of these modes of the p-vinylaniline cation in the D 0 state resemble those of the neutral species in the S 1 state.