The adiabatic ionization threshold (AIT) of trans- and gauche-benzocaine has been measured by zero electron kinetic energy-pulsed field ionization (ZEKE-PFI) spectroscopy to be 7.8412 +/-0.0008 eV ( lasers at 34134.4 and 29109.3 cm(-1)) and 7.8421 +/- 0.0004 eV ( 34144.8 + 29105.7 cm(-1)), respectively. AITs computed at the B3LYP/AUG-cc-p-VDZ level for the two conformers are some similar to 2500 cm(-1) lower than the experimental; in contrast their energy difference is very close. The trans- benzocaine cation ZEKE spectra has been recorded taking a number of S-1 intermediate vibronic states. The spectra provide an energy threshold for the appearance of intramolecular vibrational redistribution ( IVR) around similar to 540 cm(-1) in the S-1 state.