Principal component analysis is applied to 309 groundwater chemical data information from wells in the Serra Geral Aquifer System. Correlations among seven hydrochemical parameters are statistically examined. A four-component model is suggested and explains 81% of total variance. Component 1 represents calcium-magnesium bicarbonated groundwaters with long time of residence. Component 2 represents sulfated and chlorinated calcium and sodium groundwaters; Component 3 represents sodium bicarbonated groundwaters; and Component 4 is characterized by sodium sulfated with high fluoride facies. The components' spatial distribution shows high fluoride concentration along analyzed tectonic fault system and aligned on northeast direction in other areas, suggesting other hydrogeological fault systems. High fluoride concentration increases according to groundwater pumping depth. The Principal Component Analysis reveals features of the groundwater mixture and individualizes water facies. In this scenery, it can be determined hydrogeological blocks associated with tectonic fault system here introduced.