In this work, palladium tripod nanocrystals have been synthesized by mixing an aqueous solution of cetyltrimethylammonium bromide (CTAB) surfactant, Na 2PdCl 4, copper acetate, and ascorbic acid at 30 °C for 3 h. Addition of a small amount of copper ion source is critical to the formation of these tripods with a pod length reaching 100 nm. The incorporation of Cu atoms into the Pd tripods has been verified. The entire Pd tripod is single-crystalline with their branches growing along the [111] and [200] directions. Formation of side branches can be observed in some tripods. Triangular nanoplates are initially formed and evolved into the tripod structure in 20-30 min of reaction. Further growth leads to elongation of the pods. The large Pd tripods can serve as active and recyclable catalysts for a broad range of Sonogashira coupling reactions in water using a variety of aromatic halides containing electron-donating and -withdrawing substituents. © 2012 American Chemical Society.