A new method for introducing robustly bound organic functional groups on silica surfaces is developed. Compared to conventional monomer immobilization procedures, the new vinylsilane-impregnated polymer based protocol can be employed for the preparation of various organic group functionalized silicas that are stable under both acidic and basic conditions. Organic functional groups can be readily introduced by one-step Rh(I)-catalyzed hydroacylation reaction or appended by Suzuki coupling reactions.