The study is focused on the hydrogeological conditions and the chemistry of groundwater of the Vendian aquifer in the western part of the Leningrad oblast (Karelian Isthmus and the area near Sosnovy Bor town) and St. Petersburg City, where groundwater features higher radioactivity, but nevertheless it is used for drinking water supply. Data on the radiological characteristics, which have been determined in the estimation of the quality of groundwater used for drinking are generalized and analyzed. These characteristics include the gross alpha and gross beta activity and the specific activity of natural radionuclides 222Rn, 226Ra, 228Ra, 210Pb, 210Po, 238U, and 234U. The data were subjected to statistical and correlation analysis to determine the hygienic criteria for the use of groundwater of this aquifer for drinking water supply and to study the sources and the processes of formation of the natural radiological background. Groundwater quality standards were shown to be exceeded in the majority of the analyzed wells. The brackish water in the southern, deeper, part of the aquifer system was shown to have higher radioactivity and relatively high concentrations of 226Ra, 228Ra, 210Pb, and 210Po, compared with fresh water in the northern part of the territory, of which higher, though nonuniform, 222Rn activity is typical. Relationships between the radiation characteristics of groundwater are considered along with the causes of formation of groundwater radionuclide composition as a result of the higher radioactivity of the host deposits and the chemistry of groundwater; changes in the radiological and hydrochemical background groundwater characteristics from the north to the south are characterized in accordance with the subsidence of the aquifer system and an increase in the stagnation of the hydrochemical regime. The analysis of the well-known relationship between the concentrations of radium isotopes in groundwater, uranium and thorium isotopes in the host rocks, and groundwater residence time in the aquifer, along with the comparison of the available field data with calculation results, suggested the conclusion that the concentration of uranium in the water-bearing rocks in the major portion of the area under consideration is higher than its regional mean values.