Photoinitiators (PIs) are widely used in industrial polymerization and have been detected as emerging contaminants in environmental matrixes. It has been reported that humans are exposed to PIs, but the maternal–fetal transmission of PIs has not been documented. In this study, we analyzed 21 PIs (9 benzophenones, BZPs; 8 amine co-initiators, ACIs; and 4 thioxanthones, TXs) in matched maternal–cord plasma samples from 49 pregnant women in South China. Sixteen of the 21 target PIs were found in maternal plasma at concentrations of ∑PIs (sum of the detected PIs) from 303 to 3500 pg/mL. Meanwhile, 12 PIs were detected in cord plasma with ∑PIs from 104 to 988 pg/mL. The PIs detected in both maternal and cord plasma samples were dominated by BZPs, followed by ACIs and TXs. Different groups of PIs showed structure-dependent placental transfer efficiencies (PTEs). The PTEs were generally less than 100% for BZPs but greater than 100% for ACIs and TXs. By further theoretical calculation, we revealed the critical structural features of PIs that affect PTEs. This is the first study to investigate the occurrence and distribution of PIs in paired maternal and cord plasma, and it sheds light on the potential mechanism of structure-dependent placental transfer. Copyright © 2019 American Chemical Society.