We introduce a simple method to create nanosized, ordered, and highly luminescent thin film of Eu (III)-block copolymer complex. Micelles of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) in P4VP-selective solvents (ethanol/N,N-dimethylformamide (DMF) mixture) serve as nanoreactors for the synthesis of Eu(III)-block copolymer complex with the presence of 1,10-phenanthroline (Phen) as cooperative ligand. The resulted quaternary complexes were characterized by FT-IR spectra, N-15 NMR spectra, and elemental analysis, indicative of a composition of Eu(III)-(PS-b-P4VP)-Phen-5DMF. Atomic force microscopy and transmission electron microscopy investigations reveal that the Eu(III)-(PS-b-P4VP)-Phen-5DMF complex can self-organize into hexagonally ordered thin films when dip-coated from the solution onto silicon or silica glass substrates. Such ordered thin films can emit red fluorescence of Eu3+ with strong intensity and long lifetime. This method can be easily extended to prepare other ordered luminescent rare earth-polymer complexes thin films. (c) 2005 Wiley Periodicals, Inc.