Development of efficient and durable nanofibrous composite membranes for dyes separation is still a big challenge in the practical applications. Herein, we demonstrated a novel nanofibrous composite membrane consisting of electrospun poly(arylene ether nitrile)(PEN) nanofibrous substrate and bioinspired polydopamine (PDA) coated graphene oxide barrier layer for anionic dyes separation. To achieve this target, PEN nanofibrous mat was prepared by electrospinning technique and hot-pressing treatment. Thereafter, the graphene oxide nanosheets were directly assembled onto above highly porous PEN nanofibrous mat by a simple vacuum suction method. Finally, as-obtained PEN/GO nanofibrous composite membrane was further modified by bioinspired PDA coating, thus forming PEN/GO-PDA nanofibrous composite membrane. Benefiting from the superiority of hydrophilic GO-PDA skin layer and interconnected porous PEN nanofibrous supporting layer, the resultant optimized PEN/GO-PDA nanofibrous composite membrane exhibited an excellent permeate flux of 99.7 L/m(2) h (0.1 MPa, pH=3.0) and a high rejection (99.8%) for Direct Blue 14 with the concentration of 100 mg/L at 25 degrees C. This novel composite membrane demonstrated excellent mechanical strength of 28.1 MPa and achieved high temperature resistance. The rejection of Direct Blue 14 (100 mg/L) remained 92.6% and permeate flux reached 141.5 L/m(2) h as the operating temperature increased to 90 degrees C. Moreover, the resultant PEN/GO-PDA nanofibrous composite membrane exhibited good reusability after repeated operations and excellent antifouling properties (the flux recovery ratio reached 95.0% after 3 runs for 9 h). This work provides an alternative way to prepare high-performance composite membrane materials, which can deal with multiple challenges for dyes separation.