Taking the typical karst agricultural region, Xiaojiang watershed in Luxi of Yunnan Province as a research unit, utilizing the groundwater quality data in 1982 and 2004, the aerial photos in 1982 and TM images in 2004, supported by the GIS, we probe into the law and the reason of its space-time change of the groundwater quality over the past 22 years in the paper. The results show: (1) There were obvious temporal and spatial changes of groundwater quality during the past 22 years. (2) Concentrations of NH+4,SO2-4,NO-3,NO-2,Cl- and the pH value, total hardness, total alkalinity increased significantly, in which NH+4,NO-3, andof groundwater exceeded the drinking water standards as a result of non-point pollution caused by the expansion of cultivated land and mass use of the fertilizer and pesticide. (3) Oppositely, Ca2+ and HCO-3 showed an obvious decline trend due to forest reduction and degradation and stony desertification. Meantime, there was a dynamic relation between the groundwater quality change and the land use change.