Quantitative analysis of reflection electron energy loss spectra for ultrathin HfO2, Al2O3, and Hf–Al–O dielectric thin films on Si(100) were carried out by using Tougaard-Yubero [Surf. Interface Anal. 36, 824 (2004)] QUEELS-ε(k,ω)-REELS software. Experimental cross sections obtained from reflection electron energy loss spectroscopy were compared with theoretical inelastic scattering cross section Ksc deduced from the simulated energy loss function (ELF). The ELF is expressed as a sum of Drude oscillators. For HfO2, the ELF shows peaks in the vicinity of 10, 17, 22, 27, 37, and 47eV. For Al2O3, a broad peak at 22eV with a very weak shoulder at 14eV and a shoulder at 32eV were observed, while for the Al2O3 doped HfO2, the peak position is similar to that of HfO2. This indicates that when Hf–Al–O film is used as a gate dielectric in a complementary metal-oxide semiconductor transistor, its electronic structure is mainly determined by the d state of Hf. In addition, the inelastic mean free path (IMFP) was also calculated from the theoretical inelastic scattering cross section. The IMFPs at 300eV were about 7.05, 9.62, and 8.48Å and those at 500eV were 11.42, 15.40, and 13.64Å for HfO2, Al2O3, and Hf–Al–O, respectively. The method of determining the IMFP from the ELF is a convenient tool for ultrathin dielectric materials.