We demonstrated an efficient and robust approach for the preparation of polymer/quantum dot (QD) nanocomposite thin films in nonpolar media. By employing photopolymerization based on the thiol-ene reaction, thiol-containing polymer with affinity groups for CdSe@CdS QDs was produced for the buildup of the polymer/CdSe@CdS QD nanocomposite thin films utilizing layer-by-layer assembly. The polymer/QD nanocomposite films were characterized by SEM, TEM, fluorescence spectrometry, thermogravimetric analysis, confocal laser scanning microscopy and time-resolved fluorescence spectrometry. The resulting free-standing polymer/QD nanocomposite films exhibit high fluorescent intensity, moderate transparency, good photostability and thermal stability. We further applied photolithographic patterning in conjunction with an LBL assembly method to fabricate a polymer/CdSe@CdS QD nanocomposite pattern on a flexible substrate. This versatile and facile method provides prospects for the design of novel photonic devices based on the polymer/QD nanocomposite thin films.