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 Pt-Cu nanocrystals (NCs) from concave nanocubes (CNCs), to excavated nanocubes, to tripods via simply switching the amount of glycine (reducing agent). These Pt-Cu nanostructures supply a desirable platform for carrying out the structure-dependent electrocatalytic studies in the liquid fuel electro-oxidation. Impressively, all of the Pt-Cu NCs show high activity and outstanding durability for alcohol oxidation. In particular, the Pt-Cu 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.