Nanosized pyrogenic silica was used as a filler for UV/EB curable acrylates. In order to avoid highly viscous solutions due to incompatibility of the inorganic filler with the organic polymer, trialkoxysilanes were used as coupling agents. The acid catalyzed hydrolysis/condensation of trialkoxysilanes enabled favorable incorporation of silica into the acrylate matrix, thus resulting in the formation of acrylate-nanocomposite formulations with up to 35 wt.-% of silica. In this way, surface modified silica was proposed to have a ladder-like arrangement of linked siloxanes, which was demonstrated by means of multinuclear MAS NMR and MALDI-TOF mass spectroscopy. After UV or electron beam (EB) curing of such formulations, crosslinked polyacrylate nanocomposite coatings with improved properties, e.g. scratch, abrasion and heat resistance, are obtained. Therefore, the application of polymeric nanocomposite coatings is constantly increasing in the wood and plastics industry.