A modest 0.5–1 mol % amount of the sol–gel entrapped hybrid catalyst SiliaCat Pt(0) selectively mediates the hydrosilylation of different olefins under Ar atmosphere at room temperature or at 65 °C, depending on the substrate. Low levels of Pt leaching ensure minimal amounts of platinum residues in crude product and no plant contamination. Valued platinum nanoparticles remain entrapped within the organosilica xerogel that can thus be reused.