Short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) are high-production-volume persistent and toxic industrial chemicals found ubiquitously in various environmental matrices. However, information is scarce regarding human internal exposure. The congener-specific SCCP and MCCP levels in matched maternal serum (n = 31), umbilical cord serum (n = 31), and placenta (n = 31) were studied to investigate the maternal-placenta-fetus distribution and the placental transport mechanisms of SCCPs and MCCPs. The results indicated that lower chlorinated and shorter carbon chain CPs were efficiently transported across placenta compared to highly chlorinated and longer carbon chain CPs. Meanwhile, ∑MCCP concentration followed the order of maternal sera > placentas > cord sera. The cord/maternal concentration fraction ratios (RCM) of CPs exhibited similar values from C10 to C14, and then from C15, a decreasing trend was observed with increasing carbon chain length. The log-normalized maternal SCCP concentrations were positively correlated (P < 0.01) with that in the cord, suggesting fetus exposure to SCCPs during pregnancy. Furthermore, the placenta/maternal concentration fraction ratio (RPM) values for MCCPs were relatively higher than those for SCCPs, demonstrating that MCCPs were not efficiently transported and effectively retained in placenta tissues. These findings provide a better understanding of the maternal-fetal transmission and neonatal exposure to CPs.