We present a method to combine the functional features of poly(diethyl vinylphosphonate) (PDEVP) and photoluminescent silicon nanocrystals. The polymer-particle hybrids were synthesized in three steps through surface-initiated group transfer polymerization using Cp2YCH2TMS(thf) as a catalyst. This pathway of particle modification renders the nanoparticle surface stable against oxidation. Although SiNC properties are known to be sensitive toward transition metals, the hybrid particles exhibit red photoluminescence in water. The temperature-dependent coiling of PDEVP results in a change of the hydrodynamic radius of the hybrid particles in water. To the best of our knowledge, this is the first example of controlled catalytic polymerization reactions on a silicon nanocrystal surface.