Infrared reflection-absorption spectra of plasma-enhanced chemical vapor deposition (PECVD) amorphous TiO2 thin films on aluminum were obtained with s- and p-polarized light and oblique incidence angles. Such spectra were analyzed by means of spectral simulations based on a Fresnel equation for a three-layered system. The optical constants used in the simulations were obtained through the Kramers–Krönig analysis of the reflectance spectra of a pellet of powdered amorphous TiO2. LO-TO energy-loss functions were also calculated from these optical constants, and a splitting was observed. A good qualitative agreement between experimental and simulated spectra was achieved, and the Berreman effect was observed in both cases when p-polarized light was used. It was shown, therefore, that the Berreman effect makes infrared reflection-absorption spectroscopy a successful technique for the characterization of an amorphous TiO2 thin layer on aluminum.