In this study, high silica ZSM-5 was selected as an adsorbent for the removal of toluene (TOL) and n-hexane (HEX) binary mixtures from aqueous solution over a wide range of concentrations. In comparison with the single component systems, the binary mixture induced to a selective adsorption by the ZSM-5 zeolite. As a matter of fact, a selective adsorption, described by a competitive dual site Langmuir adsorption isotherm, is revealed where alkane compound is preferred to the aromatic one. Results from adsorption isotherm were related to the structural answer of the ZSM-5 framework as a function of a HEX-TOL equimolar binary mixture adsorption. Rietveld refinements provided information about the relative position of both molecules within the ZSM-5, and on the intermolecular distances between the adsorption sites of HEX and TOL. Residuals of electron density calculated by mean of delta Fourier maps indicated the presence of both guest molecules but with a clear indication of preferential towards n-hexane, and a clear differential adsorption site distribution. The occurrence of host-guest interactions in the narrow intracrystalline micropores between the solid catalyst and embedded molecules have been revealed.