We describe the application of low energy time-of-flight coincidence (e,2e) spectroscopy for measurements of the energy band parameters of a dielectric. The (e,2e) spectrometer can operate also in a single-electron mode by switching off coincidence conditions, and can be used for recording electron energy loss spectra (EELS). Thus, the combination of (e,2e) and EELS allows the measurement of energy gap E valence bandwidth DeltaE(val), electron affinity chi and excitonic levels position E-ex of a dielectric. The energy band parameters of LiF film deposited on Si(001) surface are measured: E-g = (13.0 +/- 0.4) eV, DeltaE(val) = (6.0 +/- 0.5) eV, E-ex = (10.0 +/- 0.4) eV, chi = (1.0 +/- 0.4) eV. (C) 2003 Elsevier Ltd. All rights reserved.