Crosslinked polystyrene (CPS) beads modified with polar groups for the separation of aromatic/aliphatic hydrocarbons were successfully prepared. The synthesized beads were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The effects of the crosslinking agents and polar groups on the swelling and selectivity performances toward n-heptane/toluene mixtures were studied. Impressively, the results indicated that the sulfone-modified CPS beads obtained a high toluene selectivity. Further adsorption tests with a variety of aromatic/aliphatic hydrocarbons were carried out at 50°C with initial aromatic concentrations of 13 wt %, and the results showed that the beads had a preferential selectivity for aromatic hydrocarbons, in particular, a higher separation factor of 6.76 for benzene/cyclohexane mixtures. We expect that modified CPS beads will serve as an effective material for the selective separation of aromatic/aliphatic hydrocarbons in chemical and petrochemical fields. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40156.