The objective of this paper is twofold: first, to introduce an innovative technique for extracting and exploiting the Electromagnetic (EM) waveguide dispersion of civil engineering materials by means of GPR; and second, to monitor the water ingress front during the absorption process for various concrete mixes. This technique is based on a new inversion procedure that applies the Electromagnetic Waveguide Model (WGM) to invert phase velocity dispersion curves in their modal form. A Parallel homogenization model, derived from the Lichtenecker-Rother equation, has been employed to extend the waveguide from a one-layer to a two-layer medium. The WGM outputs are then used to estimate the geometric parameters of the propagation medium and offer a primary application to water transfer monitoring in concrete through capillarity effects. The initial WGM validation is carried out on FDTD-simulated propagation signals, while the second validation relies on GPR data acquired from homogeneous materials. To achieve the second objective, a broad-based experimental study is conducted for the purpose of correlating electromagnetic waveguide dispersion parameters with both the geometric and hydric characteristics of various concrete mixes. Results obtained using the two-layer WGM serve to monitor the water ingress front during an absorption process. These results are then compared to the moisture gradients generated on cores using gammadensimetry, which is set as the reference. This procedure yields a number of trends, which in turn provide key information on the conditioning state of the studied concretes.