Water fluoride levels above the World Health Organization’s guideline (1.5 mg/L), common in overexploited aquifers, represent a health hazard. Our objective was to assess the health risks posed by exposure to fluoride in different drinking water sources in a contaminated basin in Mexico. Fluoride was measured in mutual drinking water sources and in the urine of 39 children and women. Risks were estimated through hazard quotient (HQ) by drinking water source. Dental fluorosis was assessed in the children. Mean fluoride water concentrations (mg/L) were: well, 4.2; waterhole, 2.7; bottled, 2.1; rainwater, 0.4. The mean urinary fluoride concentrations (specific gravity adjusted) were 2.1 mg/L and 3.2 mg/L in children and women, respectively. Our multiple linear regression model showed children’s urinary fluoride concentrations increased 0.96 mg/L for every 1 mg/L increase in water fluoride (p < 0.001). Dental fluorosis was diagnosed in 82% of the children, and their HQ according to drinking water source was: well, 1.5; waterhole, 1.1; bottled, 0.8; harvested rainwater, 0.3. The pervasive dental fluorosis indicates a toxic past fluoride exposure; urinary fluoride levels and HQs indicate high exposure and current health risks for most children. Drinking harvested rainwater will likely prevent most of the local fluoride exposure.