The aim of this work was to investigate the role of porous and chemical heterogeneities of activated carbons in the adsorption of naphthalene from aqueous media. A commercially available activated carbon was used as the adsorbent, and its surface heterogeneity was systematically altered by heat treatment at 450 and 850 degrees C, obtaining a series of carbons with various oxygen contents and similar surface functionalities. The results confirmed that the adsorption of naphthalene depends strongly on the pore size distribution of the adsorbent, particularly narrow microporosity. Moreover, oxygen functionalities reduced the accessibility and affinity of naphthalene to the inner pore structure via formation of hydration clusters. Consequently, the hydrophobic/hydrophilic character of the adsorbent is important, since it dominates the competitive adsorption of water. Adsorbents with a high non-polar character (i.e., low oxygen content) have proven to be more efficient for naphthalene adsorption. (c) 2007 Elsevier B.V All rights reserved.