We applied the resonant two-photon ionization and mass-analyzed threshold ionization spectroscopic techniques to record the vibronic and cation spectra of p-ethynylaniline. The cation spectra were obtained by ionizing via the 0(0), 12(1), and 1(1) levels of the electronically excited S-1 state. The band origin of the S-1 <- S-0 electronic excitation and the adiabatic ionization energy were found to be 32656 +/- 2 cm(-1) and 61270 +/- 5 cm(-1), respectively. The observed active modes result from the in-plane ring deformation, substituent-sensitive in-plane bending, and out-of-plane vibrations. (C) 2012 Elsevier B.V. All rights reserved.