This paper reports different routes combining photopolymerization of epoxy and acrylate monomers or photo sol-gel reaction yielding to organic or hybrid nanocomposites with enhanced thermomechanical properties. First homogeneous Interpenetrating Polymer Networks based on a dimethacrylate and an epoxide were straightforwardly synthesized by means of UV curing without any phase separation. Then, a dimethacrylate resin was mixed with a variable amount of a methacrylate trialkoxysilane precursor. Upon UV irradiation, a dual organic-inorganic polymerization occurred in one step leading to increased scratch resistance. The structural properties of the resulting coatings were investigated by Si solid state NMR spectroscopies. In addition, their thermomechanical behaviour was characterized by Dynamic Mechanical Analysis and scratch tests.