A natural radioactivity in thermal water was investigated based on 19 selected thermal waters from Poland. The analysed results show that the radionuclides’ concentrations in the study waters vary over a wide range. The temperature of the waters varies from above 20 °C to above 80 °C. The waters are characterised by different mineralisation, chemical compositions, and belong to different hydrochemical types. There is a good correlation between the water temperature and the depths of the aquifer formations occurrence, suggesting the thermal energy originates from the thermal geogradient. The concentration of radium is well correlated with the water mineralisation. The ratio of radium activity (226Ra/228Ra) in groundwater relates not only the ratio of uranium activity to that of thorium (238U/232Th) in aquifer formation, but also depends on the physical and chemical water properties. Based on the concentration of radon and its transport model, the radiation exposures due to inhalation of 222Rn and its progeny for employees and clients of the spa were assessed. The use of the thermal waters as a drinking resource may be problematic due to the possibility of exceeding the recommended annual committed effective dose 0.1 mSv.