Ground penetrating radar (GPR) is frequently used in pavement assessments, mainly using the evaluation of wave travel times. However, GPR data provide further information that could be used in order to determine the inner conditions and characteristics about materials. In this paper, the possible analysis of the frequency spectrum of GPR signals is analysed and discussed. Several tests were carried out in a portion of a highway in two different stages of its service life. Results highlight the relationship between the shape of the spectrum and the frequency signature with the structure and conditions of the pavement.