Surfactants have been extensively considered for decontamination of the subsurface polluted with hydrophobic organic compounds. In order to investigate the effect of molecular structures on the solubilization of hydrophobic organic compounds, solubility enhancement of two PAHs in solutions of three different surfactants-conventional, dianionic, and gemini. The batch experimental results showed that the gemini was the most effective and the dianionic was the least, indicating that organic carbon content of the surfactants was the major factor which determines the sorption capacity of surfactant aggregates in water, unlike some of the previous reports.