Well-defined noble metal nanomaterials are attractive as catalysts for various applications because of abundant surface-active sites. However, the shape-controlled synthesis of high-performance Pt-based nanocatalysts remains a forbidden challenge. We herein demonstrate a versatile approach for realizing the systemically controlled syntheses of bimetallic PtCu nanocrystals (NCs) from concave nanocubes (CNCs), to excavated nanocubes, to tripods via simply switching the amount of glycine (reducing agent). These PtCu nanostructures supply a desirable platform for carrying out the structure-dependent electrocatalytic studies in the liquid fuel electro-oxidation. Impressively, all of the PtCu NCs show high activity and outstanding durability for alcohol oxidation. In particular, the PtCu CNCs display unprecedent high activity toward MOR and EOR, which are found to be 2041.1 and 5760.9 mA mg(-1) in mass activity, 7.9- and 11.5-folds greater than the commercial Pt/C catalysts, respectively, showing a promising class of electrocatalysts for fuel cells. This work sheds great promise for optimizing the electrochemical catalysis by precisely modulating the structure of catalysts.