Due to their high surface energy, naked gold nanoparticles (AuNPs) tend to form agglomerates, which could lead to the decrease of active sites and catalytic activity of AuNPs. Herein, the gold nanoparticles/polyacrylonitrile (AuNPs/PAN) nanofibrous membranes have been prepared via an environmentally friendly and efficient route combining electrospinning, amination, and electroless plating technique. The abundant amine and imine groups can be introduced onto the surface of PAN nanofibrous membranes via amination treatment which could be used as "anchoring sites" to immobilize AuNPs. The resultant composite membranes were applied as the new catalytic materials for reduction of 4-nitrophenol to 4-aminophenol under room temperature. The new catalytic membranes exhibited the significant advantages, such as low dosage, high catalytic activity, easy recycling, and excellent stability.