The present work investigates the effect of freeze-thaw cycles on the porosity of three mixtures of road concrete containing blast furnace slag in comparison with two mixtures made with conventional materials. The main technique used in our investigations is nuclear magnetic resonance (NMR) relaxometry. This permitted the extraction of information with respect to the freeze-thaw effect on pore-size distribution, which influences both the mechanical strength and the molecular transport through the material. Moreover, by using this technique, the structure of the air voids was analyzed for the entire pore system in the cement paste and the aggregate particles. The samples under study were first dried in a vacuum oven and then saturated with water or cyclohexane where the distribution of the transverse relaxation times of the protons was recorded. The NMR relaxation measurements were performed on samples extracted from specimens maintained at 300 freeze-thaw cycles and on control samples extracted from specimens kept in water during the freeze-thaw period. Scanning Electron Microscopy (SEM) was used to analyze the microstructure of concrete samples in order to obtain information about the pore sizes and the distance between them. The results from the NMR relaxation measurements were consistent with those obtained by using standard techniques for determining the porosity and the freeze-thaw resistances. The investigations made it possible to establish the optimal composition of blast furnace slag that can be incorporated into road concrete compositions. This non-invasive technique can also complete standard techniques for assessing the porosity and the progress of internal cracks during the freeze-thaw test.