The rapid development of modern industries has caused serious water pollution such as dyes wastewater, which brings environmental problems and threatens human health. Thus, methods allowing efficient dyes removal from wastewater are substantially desirable. In this work, we fabricated graphene oxide-polydopamine (GO-PDA) by microfluidics, which enables rapid synthesis of products with excellent uniformity due to the precise control of reaction conditions. In addition, the GO-PDA/ thermoplastic polyurethane (GO-PDA/TPU) composite fibrous membrane was prepared in a high-efficiency manner by microfluidic electrospinning with a four-channel chip. Interestingly, GO-PDA not only improves the mechanical strength and hydrophilicity of the composite fibrous membrane, but also endows the membrane with efficient dye adsorption and separation capacity both for single and mixed dyes. It has been proved that the GO-PDA/TPU composite fibrous membrane exhibits selectivity towards cationic dyes, where the removal efficiency is up to 99 wt%. Moreover, the fibrous membrane could be utilized in a continuous and cyclic manner, which still maintains a high adsorption rate (>95 wt%) after 5 recycling, illustrating outstanding durability and reusability. This work proposes an efficient GO-PDA/TPU composite fibrous membrane towards selective adsorption of cationic dyes, which is of great significance in wastewater purification.