A series of SBA-15 with different modifications have been successfully prepared and applied as adsorbents to remove polycyclic aromatic hydrocarbons (PAHs) from aqueous solutions. The morphology and structural properties of the chemically modified materials are all similar to those of pure SBA-15, and thus the difference of PAHs adsorption capacity can be directly attributed to the different functional groups, which is favorable to deeply explore the adsorption mechanism. Adsorption kinetics and isotherm experiments for naphthalene (Nap), anthracene (Ant), and pyrene (Pyr) were carried out, and the results reveal that the adsorption processes follow a pseudo-second-order rate equation and the equilibrium can be achieved within 120 min for Nap and Ant, whereas only 90 min for Pyr, indicating that the more hydrophobic molecules, the easier and faster adsorption can be obtained. All of the adsorption isotherms fit well with the Freundlich model, suggesting the unevenly distributed active sites on adsorbents. The phenyl-functionalized materials possess the highest adsorption capacity, implying that the pi-pi interaction is the most primary interaction and plays the predominant role in the studied PAHs adsorption, superior to the acidic and hydrophobic interaction. Our research sheds light on the design and synthesis of advanced and highly efficient adsorbents to remove PAHs from agueous solutions.