Clay content is one of the primary causes of pavement damages, such as subgrade failures, cracks, and pavement rutting, thereby playing a crucial role in road safety issues as an indirect cause of accidents. In this paper, several ground-penetrating radar methods and analysis techniques were used to nondestructively investigate the electromagnetic behaviour of sub-asphalt compacted clayey layers and subgrade soils in unsaturated conditions. Typical road materials employed for load-bearing layers construction, classified as A1, A2, and A3 by the American Association of State Highway and Transportation Officials soil classification system, were used for the laboratory tests. Clay-free and clay-rich soil samples were manufactured and adequately compacted in electrically and hydraulically isolated formworks. The samples were tested at different moisture conditions from dry to saturated. Measurements were carried out for each water content using a vector network analyser spanning the 1 GHz–3 GHz frequency range, and a pulsed radar system with ground-coupled antennas, with 500-MHz centre frequency. Different theoretically based methods were used for data processing. Promising insights are shown to single out the influence of clay in load-bearing layers and subgrade soils, and its impact on their electromagnetic response at variable moisture conditions.