Well-defined rhodium siloxide complexes immobilized on silica ([( SiO)( SiOX)Rh(cod)1(Aerosil 200)1 and [( SiO)Rh(cod)(PCy3)](Aerosil 200) 2) synthesized via direct condensation of respective molecular precursors appeared to be very effective catalysts for quantitative synthesis of functionalized spherosilicates via direct hydrosilylation of olefins with octahydridospherosilicate. Catalyst 1 was also very active in subsequent hydrosilylation of two different olefins, which permitted efficient syntheses of spherosilicates with mixed functional groups of desired stoichiometric ratios. The catalysts were recycled at least 10 times without loss of efficiency in all the hydrosilylation processes performed. (C) 2014 Elsevier B.V. All rights reserved.