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The long-term performance of concrete structures is directly tied to two factors: concrete durability and strength. When assessing the durability of concrete structures, the study of the water penetration is paramount, because almost all reactions like corrosion, alkali–silica, sulfate, etc., which produce their deterioration, require the presence of water. Ground-penetrating radar (GPR) has shown to be very sensitive to water variations. On this basis, the objective of this experimental study is, firstly, to analyze the correlation between the water penetration depth in concrete samples and the GPR wave parameters. To do this, the samples were immersed into water for different time intervals and the wave parameters were obtained from signals registered when the antenna was placed on the immersed surface of the samples. Secondly, a procedure has been developed to be able to determine, from those signals, the reliability in the detection and location of waterfront depths. The results have revealed that GPR may have an enormous potential in this field, because excellent agreements were found between the correlated variables. In addition, when comparing the waterfront depths calculated from GPR measurements and those visually registered after breaking the samples, we observed that they totally agreed when the waterfront was more than 4 cm depth.