Manganese (Mn) is an essential nutrient; however, overexposure can be neurotoxic. Recent evidence suggests that exposure to Mn from drinking water could be neurotoxic; however, research is hampered by the lack of consensus on a reliable biomarker of Mn exposure. Naturally high concentrations of Mn can occur in groundwater, particularly for private, unregulated water systems. This study aimed to investigate the association between exposure to Mn from drinking water with a relatively low Mn content (median of 2.9 μg/L; range, undetectable–8,340 μg/L) and Mn in toenails from women collected at two time points: during and after pregnancy. Mn concentrations in the paired toenail samples gathered during the second to third trimester of pregnancy and 2 weeks postpartum were correlated (r = 0.47, p < 0.001, n = 596). Among women consuming drinking water Mn in the highest tertile (i.e., > 9.8 μg/L) significant positive correlations were found between water Mn and toenails Mn (r = 0.31 and r = 0.38, for toenail samples collected during pregnancy and postpartum, respectively), whereas little to no correlation was observed at lower water concentrations. Overall, our data suggest that maternal toenail samples are a reliable environmental Mn exposure biomarker and reflect exposure from drinking water.