This paper addresses the effect of concrete carbonation on the propagation and dispersion of electromagnetic (EM) waves and the capability of two EM, non-destructive techniques to detect this pathology. A capacitive technique operating at low frequency (around 33 MHz) and a ground penetrating radar (GPR) with a 1.5 GHz antenna were tested for the monitoring of reinforced concrete structures. To better understand the phenomena involved in concrete carbonation, the results of two complementary experimental campaigns were analyzed for saturated concretes. First, the dispersion curves of complex permittivity were measured for both carbonated and non-carbonated samples by a cylindrical coaxial EM cell. Due to carbonation, the permittivity decreased and the level of dispersion reduced slightly. Second, using GPR (coupled at approximately 900 MHz) and capacitive measurements conducted on controlled slabs, it was confirmed that the real part of the relative permittivity decreased within a range of 2 at 33 MHz and a range of 1 to 900 MHz, while the radar signal amplitude increased.