Applying femtosecond pump-probe spectroscopy at different wavelengths we demonstrate that for the indole molecule an efficient coupling does not exist between the initially excited pipi* state and the adjacent higher lying pisigma* state. This result which is in contrast to corresponding theoretical studies is represented by a stable population of the pipi* state. The analysis of the time-dependent photoelectron spectra reveals further information about the energetics of the pump and probe processes. (C) 2004 Elsevier B.V. All rights reserved.