Transparent ZrO2-polyurethane nanocomposites with high refractive index were prepared by dispersing ZrO2 nanoparticles in a polyurethane matrix via ligand molecule engineering. TEM showed that the inorganic particles were well dispersed within the polymeric network with no significant macroscopic agglomeration. By controlling the phase separation it was possible to obtain transparent zirconia nanostructured coatings, characterized by improved mechanical and thermal properties. UV-Vis spectra indicated that the coatings still maintained transparency in the visible light. The refractive index of the UV-cured films depends linearly on the ZrO2 content and varies from 1.475 to 1.625 (20 wt%) at 633 nm. These coatings could find advanced applications in coatings of optical and electronic devices.