The one‐color (1+1) resonance‐enhanced multiphoton ionization (REMPI) spectrum of the S1(1B2) state of chlorobenzene has been recorded and is similar to that obtained by other workers. Zero‐kinetic‐energy (ZEKE) photoelectron spectroscopy was then used to probe the vibrational levels in the ground electronic state of the cation (I+0) using a two‐color photoionization scheme via the S1 electronic state. By using different intermediate vibrational levels in the S1 state, different vibrations could be accessed in the ion. Vibrational symmetry selection rules for the I+0S1 ionization appear to hold well. Exciting through different S1 vibrational levels has revealed the probable mixing of the S1 normal coordinates in I+0. A previously‐identified Fermi resonance in the S1 state is also confirmed by the ZEKE spectra. The adiabatic ionization energy is measured as 73 170±5 cm−1.

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