Assembly of anisotropic nanoparticles on polymeric templates has attracted much attention recently because of the potential useful applications. In this work, 3D electrospun nanofiber membrane is used as template for the assembly of ex situ synthesized palladium nanocubes. The assembly process is achieved by simple immersion step, in which the electrostatic assembly of the nanocubes occurs. The dense nanocubes on the nanofibers as well as the fibrous nanostructure render the nanocomposite membrane excellent catalytic activity. Moreover, the catalytic membrane can be recycled for at least six times, which makes it possible for practical usage.