We determined polychlorinated dibenzodioxin (PCDD) and polychlorinated dibenzofuran (PCDF) levels in breast milk of 143 primiparae living around the three most dioxin-contaminated areas of Vietnam. The women sampled lived in the vicinity of former U.S. air bases at Bien Hoa (n = 51), Phu Cat (n = 23), and Da Nang (n = 69), which are known as dioxin hotspots. Breast milk samples from Bien Hoa City, where residents live very close to the air base, showed high levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), with 18% of the samples containing >5 pg TCDD/g lipid. However, Phu Cat residents lived far from the air base and their samples showed lower TCDD levels, with none containing >5 pg TCDD/g lipid. In Da Nang, TCDD levels in mothers from Thanh Khe (close to the air base, n = 43) were significantly higher than those in mothers from Son Tra (far from the air base, n = 26), but not other PCDD and PCDF (PCDD/F) congeners. Although TCDD levels in Bien Hoa were highest among these hotspots, levels of other PCDD/F congeners as well as the geometric mean concentration of total PCDD/F level in Bien Hoa (9.3 pg toxic equivalents [TEQ]/g lipid) was significantly lower than the level observed in Phu Cat (14.1 pg TEQ/g lipid), Thanh Khe (14.3 pg TEQ/g lipid), and Son Tra (13.9 pg TEQ/g lipid). Our findings indicated that residents living close to former U.S. air bases were exposed to elevated levels of TCDD, but not of other PCDD/F congeners.