FT-Raman spectroscopy and temperature-programmed desorption (TPD) measurements have been used to gain information on the preferred adsorption sites for p-xylene and n-heptane adsorbed within silicalite. FT-Raman spectroscopy is used to probe the location of adsorbed p-xylene, both when pure p-xylene is adsorbed and for the binary mixtures. The TPD measurements in combination with the FT-Raman spectra are used to infer the location of the adsorbed n-heptane. The results on the preferred adsorption sites for pure adsorbates are consistent with those in the literature. The results on binary mixtures show unusual behavior at loadings of four p-xylene/three n-heptane and three p-xylene/four n-heptane molecules per unit cell. In contrast to the behavior for single component adsorption, at these loadings the n-heptane molecules preferentially occupy the straight channels of silicalite, forcing the p-xylene molecules out of their normal preferred site (the channel intersections) and into the zigzag channels. The results are of importance in understanding the performance of silicalite membranes when separating gaseous mixtures of alkanes and aromatics.