A simple route for fabricating highly ordered luminescent thin films based on hybrid material of diblock copolymer and europium complex, assisted with self-organization of polystyrene-block-poly(ethylene oxide)(PS-b-PEO)diblock copolymer upon solvent annealing, is presented. PS-b-PEO self-organized into hexagonal patterns and europium complex of Eu(BA)(3)Phen was selectively embedded in PS blocks after solvent annealing in benzene or benzene/water vapor. During benzene annealing, the orientation of the PEO cylindrical domains strongly depended on the Eu(BA)(3)Phen concentration. In contrast, when the hybrid thin films were annealed in mixture of benzene and water vapor, high degree of orientation of the PEO cylindrical domains is more easily obtained, which is independent of Eu(BA)(3)Phen concentration. Furthermore, preferential interaction of PEO domains with water induces a generation of nanopores in the hybrid thin film. Atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM)were used to characterize the long-range lateral order and phase composition of the hybrid thin films. The ordered nanohybrid thin films kept the fluorescence property of Eu(BA)(3)Phen and showed a strong red emission under the 254 nm light's irradiation. The fluorescence property was confirmed by photoluminescence (PL)spectra. (C)2009 Elsevier B. V. All rights reserved.