Geochemistry of metasedimentary groundwaters and spar waters has been studied in comparison with that of granitic groundwaters in Korea. Metasedimentary groundwaters show $Ca^{2+]$-${HCO_3}^-$ type at depth and low sodium concentrations compared with granitic groundwaters, which is due to the lack of plagioclase in their aquifer mineralogy and, therefore, the predominant reaction of calcite dissolution. According to factor analysis, metasedimentary groundwaters at 100~300 m depth are represented by 1) the dissolution of calcite and Mg-carbonates, 2) transformation of kaolinite to illite, and 3) the presence of sodium as not the product of plagioclase dissolution but a artificial pollutant. Discriminant function between the granitic and metasedimentary groundwaters shows a good discriminating ability with 81.8%, and groundwaters of volcanic aquifer, which has abundant plagioclase, are included in the granitic group by this function. Spa water samples show the result of active water-rock interaction due to high temperature.