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We have developed a method to selectively deposit nanoparticles on the ordered nanoscale elements of PS–PI–PS (polystyrene– polyisoprene–polystyrene) block copolymer film. The process utilizes reactive ion plasma to selectively modify the PS surface with amine groups to electrostatically attract negatively charged Au nanoparticles. In spite of the strong interparticle Coulombic repulsion, the deposition on PS domains is significantly high. It is observed that the deposition at the edges of the domain is particularly high, forming a percolating nanoparticle necklace. The latter may lead to interesting avenues to fabricate electronic devices.