In this work, flower-like Cu/CuO (F-Cu/CuO) was synthesized using a novel method and employed as a catalyst support of Pt nanoparticles for alcohols electro-oxidation. The results confirmed that F-Cu/CuO featured a multidimensional flower-shaped structure in which Pt nanoparticles were uniformly distributed with a small particle-size distribution. Electrochemical tests revealed that the Pt/F-Cu/CuO showed a superior electro-catalytic activity and stability for alcohols oxidation, making it promising for use as an anode catalyst in direct alcohols fuel cells.