Hydrogen-plasma treatment of the polychlorotrifluoroethylene (PCTFE) film produced by radio-frequency sputtering induces considerable elimination of halogen (fluorine and chlorine) atoms. This dehalogenation produces some noteworthy structural features : surface densification (crosslinks), trapped radicals, and incorporation of oxygen in the carbon networks. These structural changes modify the vapor-sorption properties of the sputtered PCTFE film, producing a molecular-sieving effect and enhancing the polar character of solubility properties of organic vapors.