Cuprous halides are among the most studied inorganic materials for excitonic related linear/non-linear optical processes due to their large excitonic binding energies (similar to 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 CuCl(2) center dot 2H(2)O, 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 degrees 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 Z(3) excitonic absorption features. Room temperature photoluminescence measurements of all heated films reveal very intense Z(3) 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 approximate to 25-45 nm in the < 111 > orientation. The CuCl hybrid films showed bright electroluminescent emission at 384 nm when subjected to an ac voltage of about 100V peak to peak.