Previously developed technique of charge exchange ionization in a collision cell outside the ion source, which detects ions originating from the collision gas in the cell, was used to find long-lived excited electronic states of monosubstituted benzene cations. The technique is based on the criterion that charge exchange between polyatomic species is efficient only when the energy of reaction is close to zero or negative (DeltaEless than or equal to0), or the exoergicity rule. The (B) over tilde B-2(2) states of chlorobenzene, bromobenzene, benzonitrile, and phenyl acetylene cations were found to have long lifetimes (10 microseconds or longer) while excited electronic states with long lifetime were not detected for fluorobenzene, iodobenzene, toluene, nitrobenzene, and styrene cations. The long-lived states found were those displaying well-resolved vibrational structures in the photoelectron spectra. In particular, these were the states generated by removal of an electron from the in-plane nonbonding p orbitals of halogens or in-plane pi orbitals of the triple bonds.