Silicon nanocrystals are photoluminescent materials with a tremendous scope in various niche applications especially the generation of hybrid materials. Our approach for the preparation of stimuli responsive SiNC hybrid materials is based on the application of surface-initiated group-transfer polymerization. As a first step we used photografting of ethyleneglycol di(methacrylate). Then we impregnated remaining methyl acrylic surface groups with the catalyst Cp2YCH2TMS(thf). We performed polymerization studies regarding catalyst and diethyl vinylphosphonate (DEVP) concentrations, highlighting that surface grafting is dependent upon catalyst concentration and independent from added monomer amount. Furthermore, we successfully polymerized methyl methacrylate, dimethyl vinylphosphonate and diisopropyl vinylphosphonate from the SiNC surface.