Wells up to 3000 m deep at the foot of the active volcanoes Koryaksky and Avachinsky within the Avachinsky Depression revealed a basin of saline waters (up to 22 g/l), methane-rich gas (CH4 up to 75 vol% in dry gas) with a temperature up to about 70 °C in the western part of the explored area (Ketkino Field) and colder ones - to the east, closer to the Pacific coast. This article presents data on the chemical composition including trace elements, and isotopic compositions of these waters that include δD and δ18O of waters, 87Sr/86Sr of the dissolved Sr, 3He/4He, δ13C of CH4 and CO2 in gases, and δ34S of the dissolved H2S and SO4. The composition of the waters is sodium chloride, with very low contents of sulfate and magnesium in waters of the western section of the basin, high calcium (up to 960 ppm), and unusually high concentrations of strontium (up to 54 ppm). The N2/Ar ratio is generally 2–3 times higher than in the air, i.e. non-atmospheric nitrogen is present. A distinctive geochemical feature of the basin is the significant difference between δ13C–CH4 and 87Sr/86Sr in the thermal Ketkino fluids comparing to colder fluids of other parts of the basin, despite the practically identical composition of waters and gases. Possible scenarios of water-rock interaction responsible for the chemical composition of waters are discussed.