Different layers, 5, 10, 15, and 25% (w/W), of the three studied polyethylene glycols (PEGS) having different molecular weights, 600, 4000, and 20,000, were used for coating on chromosorb pink acid washed (P AW). The polarity and selectivity of the prepared packing columns and their thermodynamic parameters were determined via inverse gas chromatography. The effect of polymer-layer thickness on the polarity was studied dielectrically. The dependence of specific retention volume, enthalpy, and entropy upon the loading of polymer on support were also studied. In all investigated polymers, the loads 5 and 10% deactivate the support surface, resulting in a decrease in its capacitances, which reflects the polarity. The loads 15% PEG20,000 and 25% PEG4000 can elute n-alcohols and exhibit high efficiency of separation; however, in the case of PEG600, loading has to exceed 25% to be sufficient for eluting n-alcohols. The lower thickness of the coated polymers was preferred for good separation of saturated hydrocarbons and also for cyclohexane and aromatic hydrocarbons.