We report the formation of ordered complex nanostructures from single-layered films of mixtures of polystyrene-poly(2-vinylpyridine) (PS-P2VP) and polystyrene-poly(4-vinylpyridine) (PS-P4VP) diblock copolymer micelles by THF (tetrahydrofuran) annealing. We first examined the influence of THF vapor on PS-P2VP and PS-P4VP micelles in their single-layered films. Due to the different solubility of PS-P2VP and PS-P4VP copolymers in THF, a hexagonal array of PS-P2VP micelles was changed into cylindrical nanodomains, but that of PS-P4VP micelles was not changed. The different influence of THF on PS-P2VP and PS-P4VP micelles was combined in single-layered films of mixtures of both micelles. For the purpose, we prepared mixture solutions of independently prepared small PS-P2VP and large PS-P4VP micelles. Then, bimodal self-assemblies of micelles were prepared from the mixtures, for which the hexagonal array of large PS-P4VP micelles was surrounded by small PS-P2VP micelles. When the bimodal self-assembly was annealed by THF vapor, PS-P2VP micelles were transformed into cylindrical nanodomains, but their reorganization was guided by hexagonally arranged PS-P4VP micelles. As a result, we were able to produce ordered complex nanostructures in the form of a hexagonal array of PS-P4VP micelles surrounded by PS-P2VP cylinders, which was further utilized for the synthesis of Au nanoparticles.