We applied time of flight-secondary ion mass spectroscopy (SIMS) imaging under static conditions to investigate the interaction of electrons with a covalently bonded silane self-assembled layer of pentaflourphenyldimethylchlorosilane on Si and a physisorbed Langmuir-Blodgett film of a phospholipide dipalmitoylphosphatidylcholine on Au. Well defined surface areas of the respective layer system were irradiated with electron beams of different energies (0.5-25 keV) and different fluences (up to 3 X 10(14) electrons/cm(2)). The prebombarded surface areas were analyzed by imaging static SIMS, providing characteristic secondary ion intensities as a function of electron energies and fluences. From these results energy dependent electron induced damage cross sections sigma(e)(E) could be determined. We found a strong energy dependence of sigma(e)(E), very similar to that well known for electron induced secondary electron yields. For both investigated layers we found very similar damage cross sections sigma(e) of about 10(-15) cm(2) for 1 keV electrons. This is in contrast to the strong influence of the binding energy between the molecular overlayer and the substrate, onion induced damage cross sections ai. Our results demonstrate the general capabilities of imaging static SIMS to investigate quantitatively damaging effects in molecular overlayers and surfaces.