The adsorption isotherms of benzene revealed the low adsorption potential of polyfluoroalkyl silicas compared with both initial silica and hexadecyl silica. Hydrophobicity of all modified silicas, measured by water adsorption, was rather close at p/p(s) = 1 and was significantly different in the initial p/p(s) region: polyfluoroalkyl silicas did not nearly adsorb water but alkyl silica did it gradually. Thermodynamic,parameters of adsorption of organic compounds of different nature were studied at a zero surface coverage by gas chromatography (GC). The high enough contributions of specific interactions as well as polar molecular group increments to the Gibbs adsorption energy were found to be characteristic of polyfluoroalkyl silica. The selectivity of polyfluoroalkyl silicas and the commonly used fluorinecontaining liquid stationary phase for GC (OV-210) toward homologous ethers, esters, and alcohols was comparable in most cases. GC data, IR spectra, and adsorption measurements were in good agreement with each other. It was shown that residual SiOH-groups of silica do not nearly take part in the adsorption process because they are effectively screened by the attached organic groups.