Porous Pt-Cu alloy networks are synthesized through a one-pot hydrothermal process, with ethylene glycol as the reducing agent and the block copolymer Pluronic F127 as structure-directing agent. The structure, porosity and surface chemical state of as-prepared Pt-Cu alloy with different composition are characterized. The formation mechanism of the porous structure is investigated by time sequential experiments. The obtained Pt53Cu47 alloy possesses a unique 3D hierarchical porous network structure assembled by interconnected nanodendrites as building blocks. Because of the high surface area, concave surface topology and open porous structure, the Pt53Cu47 alloy catalyst exhibits enhanced catalytic activity towards methanol and ethanol electro-oxidation in comparison with commercial Pt black and the Pt73Cu27 alloy synthesized following the same process as Pt53Cu47. (C) 2015 Elsevier B.V. All rights reserved.