Humic fraction (HF) collected under acidic conditions and used as an adsorbent for various phosphate-based plasticizers in hexane is immobilized on silica gel. Most plasticizer analytes examined in this study under the same conditions achieved adsorption percentages above 90% in 1 h based on the difference in peak area. The Fourier transform infrared (FTIR) spectroscopy results indicate that the interaction leading to the adsorptions between the functional moieties of the analyte and HF (e.g., the carboxylate group of analyte against the carboxyl group of HF) is specific, reversible, and dipole-dipole-oriented. Moreover, it is significantly enhanced by hexane. However, the π−π interaction (even hydrogen bonding in all cases) was either not as significant or absent in hexane and, therefore, contributed little or nothing to the percentage of adsorption. The interaction is highly affected by the acidic or basic origin of the additive introduced to the liquid phase of the matrix, and it is subject to the steric hindrance effect caused by the bulky alkyl groups attached to ether linkages and the relative position of the two ether bonds on the aromatic moiety of the analyte. The pre-concentration of the analyte and, thus, the recycle of the adsorbent can be achieved by adsorbing and, subsequently, desorbing it in a different solvent, such as acetonitrile. Furthermore, the adsorption process is surface-oriented because of its dependence upon both time and the amount of adsorbent.