Cuprous halides are among the most studied inorganic materials for excitonic related linear/non-linear optical processes due to their large excitonic binding energies (~190 and 108 meV for CuCl and CuBr, respectively). In recent years, we have studied CuCl thin films deposited by vacuum evaporation and sputtering techniques on a variety of substrates. We now report on the extension of this research to the deposition of CuCl nanocrystals on flexible substrates via a spin-on technology. In this study, we present the synthesis, deposition and characterization of CuCl nanocrystals embedded in organic polysilsesquioxane (PSSQ) films on a variety of substrates via the spin coating method. The nanocrystals were synthesized by a complexation–reduction–precipitation mechanism reaction of CuCl₂ 2H₂O, alpha D-glucose and de-ionized (DI) water with a PSSQ based solution as the host matrix material. The deposited films were heated at 120 °C for durations between 1 and 24 h in vacuo. The room temperature UV–Vis absorption spectra for all hybrid films, except the as-deposited film, showed both Z_1,2 and Z₃ excitonic absorption features. Room temperature photoluminescence measurements of all heated films reveal very intense Z₃ excitonic emission at 3.221 eV. Room temperature x-ray diffraction (XRD) of the as-deposited films gave no evidence of the crystallization of CuCl. However, after heating the films, XRD confirmed the preferential growth of CuCl nanocrystals whose average size is ≈25–45 nm in the 1 1 1 orientation. The CuCl hybrid films showed bright electroluminescent emission at 384 nm when subjected to an ac voltage of about 100 V peak to peak.