We report the synthesis of nonaqueous dispersion of CdSe nanoparticles and the layer-by-layer assembly of hybrid poly(vinylpyridine) (PVP)/CdSe multilayer thin films based on hydrogen bonding. The multilayer buildup is monitored by W-vis spectra, which showed a linear increase of the film absorbance with the number of adsorbed CdSe layers. The resulted films have a high degree of flatness and smoothness as indicated by small-angle X-ray diffraction. Hydrogen bond interaction, the driving force for the formation of PVP/CdSe multilayer thin film, between the pyridine group of PVP and the carboxylic acid group on CdSe was verified by FTIR spectroscopy.