The modification of poly(trimethylsilylpropyne) (PTMSP) during the formation of its film as a stationary phase on the capillary-column wall with volatile solids (naphthalene and anthracene) allowed the performance of the chromatographic column to be substantially enhanced (for example, by a factor of two to three for isobutane). It was shown that the enhancement of column efficiency was due to an increase in the rate of interphase mass transfer of analytes in the gas-PTMSP system.