Au nanopuncheons with exposed high-index facets have been synthesized in high-yield by employing didodecyldimethylammonium bromide (DDAB) as surfactant in one-step seed-mediated growth. Transmission electron microscopy (TEM) characterization showed that the as-prepared Au nanopuncheons possessed 24 high index facets of {2 5 0}, {3 0 1}, and 2 {0 1 0} planes. Due to the high density of atomic steps and kinks in the structure, the Au nanopuncheons exhibited high surface enhanced Raman scattering (SERS) activity toward Rhodamine 6G. (C) 2014 Elsevier Ltd. All rights reserved.