Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are attracting more and more attention for the neurodevelopment toxicity effects. We evaluated the concentrations of 15 individual OH-PBDEs and 3 bromophenol (BRP) congeners in 30 mother-newborn paired placenta, breast milk, fetal cord blood, and neonatal urine samples collected from South China. The geometric mean (GM) concentrations of ΣOH-PBDEs were 37.6, 61.3, and 76.8 pg g−1 ww in placenta, breast milk, and cord blood, respectively. The GM concentrations of ΣBRPs were 47.6, 119, and 30.2 pg g−1 ww in placenta, breast milk, and cord blood, respectively. The GM concentrations of ΣOH-PBDEs and ΣBRPs in neonatal urine were 72.0 and 79.8 pg ml−1, respectively. Of the 15 OH-PBDE congeners analyzed, the three most frequently detected congeners were 2′-OH-BDE-68 (72.1%), 6-OH-BDE-47 (67.6%), and 2′-OH-BDE-28 (65.8%). The estimated daily intake (EDI) of OH-PBDEs for the breast-fed infants was 9.31±4.00 ng kg−1 bw day. The accumulation of OH-PBDEs in newborns was much lower than the estimated lowest observed-effect concentration (LOEC) of neurotoxicity. The present study provided the first systematic fundamental data that exposure to OH-PBDEs for newborn and their mothers in South China.