In this chapter, we document an extensive record of concentrations and speciation of polythionates (PTs: S 4 O 6 2− , S 5 O 6 2− , and S 6 O 6 2−), which form in the warm (21-60 °C) and hyper-acidic (pH < 1.8) waters of the crater lake of Poás volcano (Costa Rica) through interaction with gaseous SO 2 and H 2 S of magmatic origin. Our data set, together with earlier published results, covers the period 1980-2006 during which lake properties and behavior were marked by significant variations. Distinct stages of activity can be defined when combining PT distributions with geochemical, geophysical and field observations. Between 1985 and mid-1987, when fumarolic outgassing was centered on-shore, the total concentration of PTs in the lake was consistently high (up to 4,200 mg/kg). Mid-1987 was the start of a 7-year period of vigorous fumarolic activity with intermittent phreatic eruptions from the lake, which then dried out. Concentrations of PTs remained below or close to detection limits throughout this period. After mid-1994, when a new lake formed and fumarolic outgassing shifted to the dome, the total PT concentrations returned to relatively stable intermediate levels (up to 2,800 mg/kg) marking more quiescent conditions. Since early 1995, numerous weak fumarole vents started, opening up at several other locations in the crater area. During short