Poly (dialkyl vinylphosphonate)s (PDAVPs) are an interesting class of polymers due to their thermoresponsive behavior close to the physiological range. Rare Earth Metal-Mediated Group Transfer Polymerization (REM-GTP) is used to synthesize PDAVPs with narrow PDIs and high molecular weights. In further studies we have shown the functionalization of hydride terminated silicon surfaces with PDAVPs applying Surface-Initiated GTP. These surfaces exhibit a temperature dependent change of polarity. We used similar strategies to functionalize photoluminescent silicon nanoparticles with poly (diethyl vinylphosphonate) (PDEVP). Such hybrid nanoparticles still exhibit photoluminescence characteristics of silicon nanocrystals and the lower critical solution temperature effect of PDEVP above 35°C.