Abstract Five types of nanofibrous membranes were prepared by electrospinning poly( ɛ-caprolactone) (PCL), poly( d, l-lactide) (PDLLA), poly(lactide-co-caprolactone) (P(LA/CL)), poly( d, l-lactide-co-glycolide) (PDLGA) and methoxy polyethylene glycol-poly(lactide-co-glycolide) (MPEG-PLGA), respectively. These electrospun nanofibrous membranes (ENFMs) were used to adsorb anthracene (ANT), benz[ a]anthracene (BaA) and benzo[ a]pyrene (BaP) from aqueous solution, and the sorption kinetics and isotherms of these PAHs on the five ENFMs were investigated. The pseudo-second-order model (PSOM) can well describe the sorption kinetics of the three PAHs on five ENFMs, and the partition-adsorption model (PAM) can interpret the sorption processes of PAHs on the ENFMs. PCL ENFMs, which had the largest surface areas (8.57 m 2 g −1), exhibited excellent sorption capacity for ANT at over 4112.3 ± 35.5 μg g −1. Moreover, the hydrophobicity and pore volume of ENFMs significantly affected the sorption kinetics and sorption capacity of the PAHs. The main sorption mechanisms of three PAHs on the PDLLA ENFMs included hydrophobic interactions and pore-filling, while those of PCL, P(LA/CL) and PDLGA ENFMs were dominated by the hydrophobic interactions. The sorption mechanisms of MPEG-PLGA ENFMs primarily included pore-filling, hydrogen bonding interactions and hydrophobic interactions. Additionally, π–π bonding interaction was also deduced to be involved in all of ENFMs sorption systems.