Conventional UV-curable formulations consist of photoinitiators, multifunctional monomers and oligomers, reactive diluents, pigments, and additives. While photoinitiators are the key components of the formulations and responsible for the absorption of light and relevant performances (e.g., cure speed, high-percent conversion, etc.), the final properties of the cured coating are governed by the other high-volume components. With recent advances in the use of nanomaterials like metals, metal oxides, and silicates in coatings, it is now possible to prepare nanocoatings with enhanced physical, chemical, and biological properties. This is due, in part, to the difference in surface area per unit of volume at the nanoscale. Nanocoatings are usually prepared by UV irradiation of formulations containing dispersed nanoparticles. However, the homogeneous dispersion of these nanoparticles is a key challenge due to their easy agglomeration arising from their high surface-free energy. It is often difficult to obtain well-dispersed formulations providing good transmission of light for a complete cure. In this article, we report several synthetic methodologies for the preparation of epoxy and (meth)acrylate-based nanocoatings containing clay or metal nanoparticles. In the former case, photolysis of intercalated photoinitiator within the layers of montmorillonite clay in the presence of monomers resulted in the in situ formation of exfoliated structures. For the preparation of metal nanocoatings, the formation of silver or gold nanoparticles and crosslinking are accomplished simultaneously by photoinduced electron transfer and polymerization processes. The nanoparticles are homogenously distributed in the network without macroscopic agglomeration. Applicability to both free radical and cationic systems is demonstrated. Moreover, a novel photochemical route for grafting from the self-assembled monolayers on gold is presented.