In this study, a set of 15 bisphenols (BPs) and one emerging derivative (4-hydroxyphenyl 4-isoprooxyphenylsulfone, BPSIP) were analyzed in 60 pairs of maternal plasma, cord plasma, and placenta samples from pregnant women in South China. A total of 4 of the 15 target BPs, i.e., BPA, bisphenol S (BPS), bisphenol AF (BPAF), and bisphenol E (BPE), were frequently detected in the three human biological matrixes. The derivative BPSIP was identified in all maternal plasma samples at unexpectedly high levels, second only to BPA. The concentrations of bisphenols in maternal plasma were slightly higher than in cord plasma for BPA, BPS, and BPE but much higher for BPSIP and much lower for BPAF, indicating that the five frequently detected bisphenols have different placental transfer behaviors. The placental transfer efficiencies (PTEs) of BPA, BPS, and BPE were similar, which were significantly higher than the PTE of BPSIP. The PTE of BPAF was much higher than other BPs, indicating its strong maternal transfer and high fetal accumulation. The PTEs of bisphenols were structure-dependent, and passive diffusion was suggested as the potential mechanism of placental transfer. Significant concentration correlations of the five major bisphenols between maternal plasma and cord plasma were observed (p < 0.05). Meanwhile, significant associations of BPAF concentrations in maternal/cord plasma with some maternal characteristics and adverse birth outcomes were also identified (p < 0.05).