In this work, a facile and low-cost preparation of polypyrrole-modified multi-walled carbon nanotubes (MWCNTs) supported palladium/copper alloyed nanocubes catalysts have been successfully synthesized. To increase the stability and utilization ratio of the noble metal, a two-step strategy was employed, which included the synthesis of a polypyrrole-MWCNTs composite and the preparation of a hollow palladium/copper alloyed nanocubes catalyst. Ppy-modified MWCNTs composite was produced through carbonization of polypyrrole on the MWCNTs surface to be used as a catalyst support. Hollow PdCu alloyed nanocubes were successfully supported on ppy-modified MWCNTs by a novel one-pot template-free strategy. The novel H-PdCu/PPy-MWCNTs hollow nanocubes catalyst was about 50 nm in diameter. The catalysts with 10% Pd showed a very high electrochemically active surface area and significant increase electrocatalytic activity toward the alcohols oxidation (Fig. 1), which make it the preferable catalysts for direct alcohol fuel cells.