Understanding the combined effect of soil organic matter (SOM) and surfactants on the partitioning of hydrophobic organic compounds in soil/water systems is important to predict the effectiveness of surfactant-enhanced remediation (SER). In the present study we investigate the partitioning of hexachlorobenzene (HCB) within a humic acid (HA)-coated kaolin/Triton X-100 (TX100)/water system, with special emphasis on the interaction between TX100 and HA, and their combined effect on HCB sorption. HA firstly enhanced then suppressed TX100 sorption to kaolin as the amounts of HA increased, while the addition of TX100 led to a consistent reduction in HA sorption. In the HA-coated kaolin/TX100/water system, TX100 played a primary role in enhancing desorption of HCB, while the role could be suppressed and then enhanced as HA coating amounts increased. Only at HA coating above 2.4%, dissolved HA outcompeted clay-bound HA for HCB partitioning, resulting in dissolved HA enhanced desorption. The presence of dissolved HA at these conditions further promoted the effectiveness of TX100 enhanced desorption. Despite a reduced TX100 sorption to clay was achieved due to the presence of dissolved HA, the effect on HCB desorption was comparatively slight. A reliable cumulative influence of HA and TX100 on HCB desorption was observed, although HCB desorption by HA/TX100 mixed was less than the sum of HA and TX100 individually. Our study suggests that for soils of high organic contents, the combined effect of SOM and surfactants on HOCs desorption can be applied to improve the performance of SER. (C) 2011 Elsevier B.V. All rights reserved.