The fluoride-catalysed hydrolysis of mixtures of CH3Si(OCH3)(3) and Mg(OC2H5)(2) in the presence of preformed nanosized R4N+Br--stabilised Pd colloids results in the formation of micro/mesoporous hydrophobic sol-gel materials in which the Pd clusters are entrapped individually in the solid matrix. The materials are active catalysts in the hydrogenation of 1,5-cyclooctadiene.