Systematic determination of and adsorption experiment on fluorine in the carbonate rock|soil|water system in the karst region studied in Guizhou Province, in conjunction with the mineral surface and soil chemistry data, have revealed the geochemical characteristics of F and the mechanisms of its transport and enrichment in the rock|soil|water system of the karst region, central Guizhou Province. Deep|seated underground waters (-100m or lower) and soil layers in the karst region of central Guizhou are characterized by high|F anomalies whereas shallow|level underground and surface waters by low contents of F (mostly lower than 0.5 mg/L). Fluorine in soil and water in the region studied comes largely from Triassic marine strata dominated by gypsum|bearing carbonate rocks. The special adsorption and desorption of F on the surface of geothite in soil layers are the important mechanisms of its transport and enrichment in the rock|soil|water system of the karst region studied. Systematic determination of and adsorption experiment on fluorine in the carbonate rock | soil | water system in the karst region studied in Guizhou Province, in conjunction with the mineral surface and soil chemistry data, has revealed the geochemical characteristics of F and the mechanisms of its transport and enrichment in the rock | soil | water system of the karst region, central Guizhou Province. Deep | seated underground waters (-100m or lower) and soil layers in the karst region of central Guizhou Fluorine in soil and water in the region is derived substantially from Triassic marine strata dominated The special adsorption and desorption of F on the surface of geothite in soil layers are the important mechanisms of its transport and enrichment in the rock | soil | water system of the karst region stud ied.