A precursor film has been fabricated from TGA (thiolglycolic acid)-stabilized CdTe nanoparticles and NDR (nitro-containing diazoresin) using electrostatic interactions and the standard layer-by-layer assembly method; covalent bonds are formed under ultraviolet irradiation. XPS provided evidence for the presence of CdTe nanoparticles within the polymer ultrathin films. UV-visible spectroscopy and FTIR spectroscopy provide evidence for the formation of a covalent linkage. Moreover, the UV-visible spectroscopy and AFM measurement support the improvement of the stability of the hybrid organic/inorganic film toward polar solvents when the linkages between the nanoparticles and polymer changed from ionic bonds to covalent bonds.