Nanomaterials with particular nanostructures which usually possess special properties always attract considerable attention. A novel bimetallic Pt/Cu hexapod nanostructure was prepared by a facile one-pot strategy. The formation mechanism was investigated by the time sequential evolution experiments and the hexapod concave nanostructures originated from the Pt/Cu rhombic dodecahedron. Further electrochemical measurements indicated the bimetallic Pt/Cu hexapod concave nanocrystals showed enhanced catalytic activities. It is believed that these novel nanostuctures would open up new opportunities for catalytic applications.