In this study, a nanosecond‐pulsed discharge plasma is employed to modify the macroporous XAD‐2 resin to improve the adsorption performance of polycyclic aromatic hydrocarbons. After modification, XAD‐2‐20 resin shows great advantage on naphthalene (Nap) adsorption, whose adsorption capacity increased by 80.6% and 43.5% compared with the raw and XAD‐2‐30, respectively. The physiochemical properties of XAD‐2 resin are characterized by scanning electron microscope, N2 adsorption/desorption, X‐ray photoelectron spectroscopy, and Fourier‐transform infrared (FTIR) spectrum. The amount of micro‐mesoporous with a size of 2–3.5 nm are formed and many carbonyl groups (C═O) and ester or carboxylic groups (O–C═O) are introduced on the XAD‐2‐20 surface, and the value of O/C is increased from 14% to 53% compared with the raw resin.