Nanostructured organic–inorganic hybrid epoxy coatings containing zirconia domains were obtained via a cationic UV/thermal dual-cure process. Uniform distribution of the in situ generated zirconia within the polymeric network on a nanometric scale (5–25nm) was demonstrated by AFM and TEM analyses. The UV-cured films showed increase of the refractive index by increasing the zirconium tetrapropoxide content in the photocurable formulation. Coatings with a drastic cut-off in the UV spectra still maintaining transparency in the visible light were achieved. These coatings could find advanced applications as antireflection coatings, or in the optical industry.