A simple process of solvent annealing has been shown to produce ordered self-assembly structures of poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP)/poly(4,4 '-oxydiphenylenepyromellitamic acid) (POAA) block copolymer/homopolymer blends in thin film, where POAA chains selectively interact with P4VP blocks by strong interpolymer hydrogen-bonding. By simply exposing the thin film to benzene/NMP (0.97/0.03, in volume) vapor mixture, ordered microphase-separated structures with PS spherical microdomains distributed within P4VP/POAA complexes matrix were obtained. The formation of the microphase-separated structures could be attributed to the substantial mobility of PS blocks and P4VP/POAA complexes and enhanced repulsion between them under the benzene/NMP mixture vapor. When the volume ratio of benzene to NMP increased to 0.98/0.02, the increasing benzene in the mixture vapor induced the adhesive collision of spherical microphase-separated structures to form long "pearl necklaces". With increasing volume ratio of benzene to NMP to 0.99/0.01, an ordered "pearl necklace" array oriented parallel to the film surface formed. The self-assembly structures were studied by FTIR spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy (TEM). Finally, possible mechanism of self-assembly and formation of microphase morphology was proposed. (C) 2010 Elsevier Ltd. All rights reserved.