More than 200 million people worldwide, including 11 million in the US, are estimated to consume water containing arsenic (As) concentrations that exceed World Health Organization and US EPA standards. In most cases, the As found in drinking water wells results from interactions between groundwater and geologic materials (geogenic contamination). To that end, we used the NCWELL database, which contains chemical information for 117,960 private drinking wells across North Carolina, to determine the spatial distribution of wells containing As contaminated water within geologic units. Specific geologic units had large percentages (up to 1 in 3) of wells with water exceeding the EPA As maximum contaminant level (MCL, 10 μg/L), both revealing significant variation within areas that have been previously associated with As contamination and identifying as yet unidentified problematic geologic units. For the 19 geologic units that have >5% of wells that contain water with As concentrations in exceedance of 10 μg/L, 12 (63%) are lithogenically related to the Albemarle arc, remnants of an ancient volcanic island, indicating the importance of volcanogenic materials, as well as recycled (eroded and deposited) and metamorphosed volcanogenic material. Within geologic units, wells that have As concentrations exceeding 10 μg/L tended to have pH values greater than wells with As concentrations less than 10 μg/L, emphasizing the importance of the extent of interaction between groundwater and geologic materials. Using census information with the geologic-based exceedance percentages revealed the importance of regional geology on estimates of population at risk compared to estimates based on county boundaries. Results illustrate that relating As contamination to geologic units not only helps explain sources of geogenic contamination but sharpens the identification of communities at risk for exposure and further illuminates problematic areas through geologic interpretation.