Electronic absorption spectra of the low-lying pipi(*) and pisigma(*) states of several aminobenzonitriles and 4-dimethylaminobenzethyne have been studied by time-resolved transient absorption and time-dependent density functional theory calculation. In acetonitrile, the lifetime of the pisigma(*)-state absorption is very short (picoseconds or subpicosecond) for molecules that exhibit intramolecular charge transfer (ICT), and very long (nanoseconds) for those that do not. Where direct comparison of the temporal characteristics of the pisigma(*)-state and the ICT-state transients could be made, the formation rate of the ICT state is identical to the decay rate of the pisigma(*) state within the experimental uncertainty. These results are consistent with the pisigma(*)-mediated ICT mechanism, L(a) (pipi(*))-->pisigma(*)-->ICT, in which the decay rate of the pisigma(*) state is determined by the rate of the solvent-controlled pisigma(*)-->ICT charge-shift reaction. The pipi(*)-->pisigma(*) state crossing does not occur in 3-dimethylaminobenzonitrile or 2-dimethylaminobenzonitrile, as predicted by the calculation, and 4-aminobenzonitrile and 4-dimethylaminobenzethyne does not exhibit the ICT reaction, consistent with the higher energy of the ICT state relative to the pisigma(*) state.