Gold nanoparticles (NPs) coated with thiol-terminated polystyrene chains of varying molar mass were added to polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymer monolayers at the air-water interface. Composite films were transferred to solid substrates by the Langmuir-Blodgett technique. For most of the investigated systems, TEM micrographs and AFM images reveal the formation of 2D island-like aggregates of particles organized on a close-packed hexagonal lattice. This characteristic aggregate formation is lost when PS ligands are within the same length regime as the PS block from the copolymer. The results are compared with those obtained for analogous systems containing no copolymer where NPs are deposited on either a bare water surface or bare glass. Interparticle distance between NPs is found to depend on the surface on which they are deposited, the presence or not of the copolymer monolayer, and ligand length. (C) 2014 Elsevier Inc. All rights reserved.