Perfluoroalkyl and polyfluoroalkyl substances (PFASs) can be transferred from a mother to her fetus during pregnancy and adversely affect fetal development. However, the efficiency and influencing factors of PFASs maternal-fetal transfer remain unclear. We measured the levels of six perfluoroalkylcarboxylates, three perfluoroalkylsulfonates, and one sulfonamide in 369 pairs of maternal and umbilical cord serum and examined the transplacental transfer efficiency (TTE) of PFASs by the functional group and carbon chain length in a prospective birth cohort in Shandong, China. All ten PFASs were detected in both maternal and umbilical cord serum in nearly all samples. Maternal and cord levels were closely correlated (the correlation coefficient [r] ranging from 0.485 to 0.908) in most PFASs except perfluorobutane sulfonic acid (PFBS) (r = 0.159). TTE was significantly affected by the functional group and carbon chain length. Compared to perfluoroalkylcarboxylates, perfluoroalkylsulfonates had a lower ratio of maternal to fetal transfer. A U-shaped relationship between carbon chain length and TTE was observed for perfluoroalkylcarboxylates while a monotonic descending trend was identified between TTE and the increasing carbon chain length for perfluoroalkylsulfonates. PFASs can readily pass through the placenta. The functional group and carbon chain length are important determinants for the TTE of PFASs.