Special morphological noble metal-based bimetallic alloy nanostructures became popular for methanol oxidation reaction in order to reduce the high cost of the Pt catalyst and improve the catalyst activity. Herein, we developed a facile one pot hydrothermal method for the synthesis of platinum-copper bimetallic nanoflowers (Pt-Cu NFs) in the presence of hexadecyl trimethyl ammonium bromide (CTAB). The morphology, structure and composition of Pt-Cu NFs were carefully characterized and the synthesized parameters were optimized systematically by adjusting different experimental conditions. Results showed that the CTAB usage and the NaI amount were critical to the controlled synthesis of Pt-Cu NFs. The Pt-Cu NFs were high-performance electrocatalysts for the methanol oxidation reaction (MOR) with superior activity and superior stability in alkaline solution, which were far better than pure Pt nanoparticle electrocatalysts.