Evidence is presented which indicates that the photoinduced intramolecular charge transfer (ICT) in 4-dimethylaminobenzonitrile proceeds by a new mechanism in which pisigma(Cequivalent toN)* state is the intermediate of a consecutive process that takes the initially excited pipi* state to the fully charge-separated ICT state. The absence of the ICT-state formation in 4-aminobenzonitrile is attributed to the smaller electron-donor strength of the amino group relative to the dimethylamino group, which hinders the pisigma*-->ICT charge-shift reaction. (C) 2004 American Institute of Physics.