Silicon wafers have been silylated with VTMS (vinyltrimethoxysilane) and hydrolyzed. Subsequently, PVP (polyvinyl pyrrolidone) was grafted onto the silylated surface by two different techniques: the grafting-through (GT) and the grafting-onto techniques (GO). The measurement of contact angles along with the topography analysis by atomic force microscopy (AFM) has allowed monitoring the different stages of the process and the temporal evolution of polymer grafting. The results have demonstrated the feasibility of both methods of grafting but have shown that the GT method gives a higher density of polymer-grafted chains. The AFM technique in adequate liquid environments has been proven to permit the surface density of chains to be distinguished by both methods and to estimate the length of the resulting PVP chains.