A radiological and hydrochemical study has been conducted on thermal and fresh groundwater samples of northern Euboea Island and eastern central Greece. Both areas are characterized by complex geology and are renowned since antiquity for their hot springs, that are exploited for therapeutic spa purposes until today. The aim of the study was to combine radiological and hydrochemical data in order to achieve a holistic water quality assessment with insights into the geology of the study areas. All samples were characterized with respect to their major and trace ion and element composition, as well as activity concentrations of Rn,Ra, Ra,Th, and K. The samples demonstrated elevated natural radioactivity and U concentrations, especially in some locations of the Kamena Vourla area, reaching 179 Bq/LRn, 2.2 Bq/L Ra, 2.9 Bq/LRa, and 17 μg/L U. The estimated circulation depth of thermal groundwater ranges between 250 m in central Greece and 1240 m in north Euboea study area, whereas the calculated water residence times range between 27 and 555 years. Our data suggest the possible presence of an unknown until know U-rich plutonic rock formation in Kamena Vourla area and immiscibility of the fresh and thermal groundwaters in the studied areas.