The present work reports the incorporation of the ZnO doped diblock copolymer matrix and its conversion into a self‐assembled structure. The diblock P(HEMA)80‐b‐P(N‐PhMI)20 and P(HEMA)90‐b‐P(St)10 copolymers consist of a majority (HEMA) and minority (N‐PhMI or St) block. The copolymers were synthesized with a block repeat unit ratio by atom‐transfer radical polymerization (ATRP) using a poly(2‐hydroxyethylmethacrylate)‐Cl/CuBr/bipyridine initiating system. The P(HEMA)‐Cl was prepared by reverse ATRP1. The average theoretical number molecular weight (Mn,th) was calculated from the feed capacity. The composite of the inorganic nanoparticles was achieved at room temperature in the liquid phase, using ZnCl2 precursor dopant and wet chemical processing to convert to ZnO nanoparticle films. Thermal characterization was performed using differential scanning calorimetry (DSC) and thermogravimetry (TG). The proton/area relationship confirmed the block copolymer compositions calculated by elemental analysis, consisting of a majority and minority blocks. Morphology properties of the polymer samples were investigated by scanning electron microscopy (SEM). The microphotographs of the film's surfaces show that the film's upper surfaces were generally smooth with ordered structure morphology. FT‐IR spectroscopy confirmed the association of the ZnCl2 precursor with the majority block and the formation of ZnO, the white SEM showed the morphology of ZnO nanoparticles' films when the surface relief changes principally due to surface loss rather than its orientation. Copyright © 2009 John Wiley & Sons, Ltd.