The main sources of radon in the air of dwellings are soil, building materials, and groundwater. This study aimed to determine the exhalation rate of 222Rn from samples made of concrete and cement mortars, as well as to evaluate by means of gamma spectrometry the hazard indexes associated with other radionuclides present in the studied samples of building materials. The results obtained allowed the comparison of the exhalation rate of radon using theoretical calculations based on one-dimensional and three-dimensional models. Measurements of the activity concentration of radon in air was performed by AlphaGuard radon detector. Furthermore, obtained results were compared with the measurements performed inside the concrete test cells. These test cells were built with the aim of simulating a dwelling in small dimensions and to evaluate indoor radon activity associated with concrete. Consequently, the obtained results of radon exhalation rate, in becquerel per meter squared per hour, for the concrete was 2.55 ± 0.03 Bq·h−1·m−2 for the 1D model and 0.461 ±0.008 Bq·h−1·m−2 for the 3D model. The exhalation rate of radon, for the cement mortar was 1.58 ± 0.03 Bq·h−1·m−2 for the 1D model and 0.439 ± 0.011 Bq·h−1·m−2 for the 3D model. The indoor concentration of 222Rn from the test cell was 112 ± 9 Bq/m3. These values were below the limit of 300 Bq/m3 recommended by the International Commission on Radiological Protection (ICRP) and <148 Bq/m3, the limit recommended by the US Environmental Protection Agency (US EPA). Even so, these values should be the subject of concern since that activity is related only to the contribution of concrete walls.