An experimental investigation of nanometric thin films by a picosecond ultrasonic technique is presented. A photoelastic model is used with an interferometric device, combined with ultrafast optical pump and probe setup, to measure the thicknesses of submicrometric layers made of TiN, Ti, and AICu deposited on silicon (Si) wafers. The results are in good agreement with ellipsometry measurements showing that the picosecond ultrasonic technique can give accurate results even when the reflectance signal is very low. Additional important results are first, that the adhesion of the TiN surface film is probed by processing both the frequency and the damping of the oscillation of a resonance acoustic mode; and second, the presence of a thin buried TiN layer under an opaque AICu film is highlighted by the interferometric setup.