A TSPM-modified silica has been prepared and employed as a filler in LDPE films, in which a photo-grafting reaction between polymerizable groups present on the functionalized filler and the polymer has been performed with the aim of obtaining stable composites with improved properties. Besides FT-IR, TGA and SEM characterization, both the TSPM-modified silica and the polymer-filler blends have been extensively investigated by means of solid state NMR, through a combined analysis of several high- and low-resolution experiments, performed on 29 Si, H-1 and C-13 nuclei. This allowed us on one hand to obtain detailed and quantitative information on the silica functionalisation reaction and on the other hand, to get an insight into the change of the dynamic properties of LDPE due to the presence of the filler. The NMR results and several macroscopic properties of the blend LDPE - silica - TSPM, such as Young's modulus and oxygen permeability, were compared with those of the corresponding blend prepared with unfunctionalized silica.