Gemini surfactants, an innovative class of amphiphilic molecules, are of increasingly scientific interest due in part to their effectiveness in soil/water remediation. This study was carried out to investigate the overall partitioning of three representative polycyclic aromatic hydrocarbons (PAHs) in the soil-water-surfactant system which takes into consideration the soil-sorbed cationic Gemini surfactant, presence of Gemini micelles, and related developed coefficients. The results indicated that the adsorption of Gemini surfactants onto soil particles through both cation exchange and hydrophobic interaction contribute to the bi or multilayer formation. The sorbed C12-3-12 studied herein, is a highly effective partitioning media for PAHs to adsorb onto the soil phase from the aqueous phase and thus, can be considered as a good adjuvant for an enhanced sorption zone. The partitioning behavior of PAHs in the soil-water-Gemini surfactant has a strong relationship with their K-ow. The experimental results from this research will be used to gain an understanding of the effect of cationic Gemini surfactant on the distribution of HOCs in a soil-water system and provide some fundamental and valuable information in remediation of contaminated soils and waters.