Whereas static conductance of molecules arranged in self-assembled monolayers has been extensively studied, little is known about the dynamics of the charge transfer in these systems. By the example of alkanethiolate films, we show that the latter phenomena can be successfully addressed by resonant Auger spectroscopy, using the core hole clock method. The charge transfer pathway was unambiguously defined by resonant excitation of the nitrile tailgroup attached to the alkyl backbone. Extension of this approach to other functional groups is possible, leading to new information valuable for molecular electronics and other applications. (C) 2007 Elsevier B.V. All rights reserved.