In this paper, the evaluation of the Rn-222 radioactivity content in drinking water samples from the Calabria region, southern Italy, is reported as a case study. The Rn-222-specific activity in the analyzed groundwater samples for human use was evaluated by using the PerkinElmer Tricarb 4910 TR setup and compared with the parameter value (100 Bq L−1) reported in the reference Italian legislation, i.e., D.Lgs. 28/2016, derived from the European Directive 2013/51/Euratom. The radiological health risk for the population of the investigated area, due to the ingestion and inhalation of Rn-222 dissolved in water, was then evaluated by calculating the total annual effective dose, only in those cases where the parameter value was exceeded. The obtained results represent a main reference for the investigated area and are useful for determining any possible radiological health risk for human beings related to the ingestion of the investigated radionuclide. Moreover, they can also be used as a baseline for future investigations regarding background radioactivity levels.