We propose a method based on high-resolution electron-energy-loss spectroscopy to measure in situ the neutral fragmentation products arising from the impact of low energy electrons on thin solid films at low temperature. We show more particularly that the detection of electronic states from a dissociation product is a good alternative when the corresponding vibrational levels are obscured by those of the deposited film. In the case of thin methanol film condensed at 18 K, we find that low energy electrons can dissociate the CH3OH molecules into CO fragments that remain within the film. The production of CO fragments, clearly identified from its lowest electronic state a (3) Pi, is studied as a function of the electron dose, electron energy, and film thickness. The energy dependence of the CO production rate, which is also calibrated in terms of an electron total scattering cross section sigma(p), is characterized by an energy threshold at 8eV, a shoulder at about 11.5 eV, a broad maximum centered around 14 eV, and a rise above 19 eV. A value of sigma(p) approximate to 4.2 x 10(-18) cm(2) is Obtained at 14 eV. The shoulder and the broad maximum are specifically attributed to the ...(6a')(1)(3sa')(2),(2)A', ...(1a '')1(3sa')2(,2)A '', and ...(5a')(1)(3sa')(2),(2)A' core excited electron resonances, which decay into their parent repulsive states. The rise above 19 eV is correlated to the lowest dissociative photoionization processes known to produce neutral CO in the gas phase. (C) 1997 American Institute of Physics.