Chemical vapor deposition (CVD) of Si(OCH 3) 4 was carried out on silicalite crystals in order to control the pore-opening size. Due to the non-acidity, relatively high temperature such as 773 K was required to deposit thicker silica layers sufficient for obtaining selective adsorbents. Adsorption of linear and branched alkanes on silicalite and CVD-silicalites was performed gravimetrically and chromatographically at about 298 K. Both methods showed that adsorption behavior was almost unchanged for hexane and butane on CVD-silicalites but the adsorption for 2-methylpentane and 2-methylpropane was suppressed with the increase of the silica amount on silicalite. The extent of suppression depended upon the length of paraffins and the amount of deposited silica on silicalite. Thus, linear and branched paraffins can be separated by choosing the extent of silica deposition on silicalite.