Self-standing thiol-functionalized fibrous membrane with bimodal pore structure was successfully fabricated through the combination of electrospinning and surfactant-directing pore formation technique. We also found that the interference of electric field as well as the rapid solvent evaporation during the electrospinning process has a negative effect on the formation of ordered mesoporous structures. As high-performance adsorption-based filtration system, such hierarchically structured membrane is found to efficiently remove Cu (II) ions under high flux.