We report a simple aqueous-solution route to synthesize hybrid Ag2S-Ag3SBr superionic conductor nanoparticles with faceted-spherical and polyhedral morphologies at low temperature. The morphological control was achieved by adjusting the 14 concentration in the presence of cetyltrimethylammonium bromide, which was used as both a Br- source and a capping reagent. The hybrid nanoparticles could self-organize into large-scale ordered arrays, and have potential applications in fabricating photonic crystals, mixed superionic conductors, high energy density batteries and near-infrared photoluminescent devices. (C) 2010 Elsevier Inc. All rights reserved.