Solubility of BTEX compounds was determined in aqueous solutions of natural CDs (α-, β-, γCD) as well as of some industrial βCD derivatives (RAMEB, HPBCD, AcβCD) measured by UV photometry. From the phase solubility diagrams the complex association constants were determined. The βCD derivatives increased the solubility of individual monoaromatic compounds, depending on the structure of the guest molecule. We have found that RAMEB (randomly methylated βCD) and AcβCD (partially acetylated βCD) are the most effective solubilizers while the effect of natural CDs is not significant because the complexes precipitate from the solutions. Extraction experiments were performed to see how the complexation of components influences the extraction using a mixture modeling the composition of these pollutants in soil. We have found that although the soluble CD derivatives are not as selective as expected based on complex association constants, they increased the efficacy of extraction by 4–6 times. The reason of the low selectivity is that the concentration ratio of certain BTEX compounds in CD solutions is smaller than in water. CD derivatives seem to have an equalizing effect: the solubility of the least soluble p-xylene is improved in the highest extent, but that of benzene the least. This result, however, is an advantage in the application of these CD derivatives in soil remediation (the availability of each BTEX compounds will be enhanced).