Self-assembled poly(4-vinylpyridine)-grafted gold (Au) nanoparticles (NPs) and polystyrene-b-poly(4-vinylpyridine) block copolymers were fabricated by the introduction of a selective solvent to a common solution. The assembled mixtures were spin-coated onto solid substrates to fabricate composite gold/polymer thin films composed of copolymer-hybridized Au NPs and independent copolymer micelles. The obtained composite Au thin films had variable localized surface plasmon resonance (LSPR) bands and microscopic morphologies upon vapor annealing with selective solvents because the adsorption and dissolving of solvent molecules into the films could rearrange the copolymer block. The hybrid nano-structured Au thin films may have potential in vapor sensing and organic assays. (C) 2010 Elsevier Inc. All rights reserved.