Early life exposure to inorganic arsenic (iAs) has been shown to interfere with foetal and early childhood development, and is associated with morbidity and mortality in adulthood. The purpose of this study was to evaluate exposure to As in utero, to determine the association between maternal and cord blood of As and birth outcomes in South African populations. Total arsenic was measured in maternal blood of a total cohort (n=650) and in paired cord blood and urine of a subset cohort (n=317). Overall, the geometric mean (GM) of As in maternal blood was 0.62μg/L (n=650; 95% CI, 0.58-0.66). In the subset cohort, the GM of maternal blood As was 0.96μg/L (n=350; 95% CI, 0.91-1.02); in paired cord blood, the GM was 0.78μg/L (n=317; 95% CI, 0.74-0.83); and in urine (creatinine-corrected), the GM was 14.26μg/g creatinine (n=317; 95% CI, 12.64-16.09). A linear correlation was found between log maternal blood As and log cord blood As (rho=0.80, p<0.001). Birth outcomes showed geographical differences. in gestational age (p<0.001), birth length (p=0.019), head circumference (p<0.001), Apgar score at 5min (p<0.001) and parity (p<0.002). In a multivariate analysis, no association between maternal blood (AsB) levels and birth outcomes were found. However, the lower the gestational age, the higher the levels of maternal AsB (β=-0.054; 95% CI-0.087 to -0.020) and mothers who had had at least one child were less likely to have higher AsB if compared to those who had never had any child (β=-0.177; 95CI-0.322 to 0.031). In both univariate and multivariate analyses, being single, and drinking water from communal outdoor taps, boreholes and rivers was associated with higher As levels. The findings suggest that more research is needed to evaluate the impact of low level As exposure on postnatal development.