A flexible and free-standing graphene oxide and nylon 6 (GO@nylon 6) multilayer nanofiltration membrane was prepared by a layer-by-layer assembly process. The combination of electrospinning and electrospraying technique was employed, which can facilely prepare large-area membrane with size of 20x30 cm. The mechanical stability of multilayer membrane has enhanced significantly due to the tightly locked structure achieved by nylon 6 nanofibers network. The novel GO@nylon 6-13 multilayer nanofiltration membrane demonstrated a pure water flux up to 11.15 Lm(-2) h(-1) bar(-1), while keeping high organic dye rejection rate (> 95% for methylene blue, and > 99% for methyl orange). The rejections rate of the Na2SO4, NaCl, CuSO4, and Pb(NO3)(2) were 56.5%, 27.6%, 36.7%, and 18.9%, respectively. Furthermore, GO@nylon 6-13 multilayer nanofiltration membrane also demonstrated a high flux of some common organic solvents (8.4, 5.3, and 0.8 Lm(-2) h(-1) bar(-1) for methanol, ethanol, and NMP, respectively), showing excellent chemical stability for separation process in those solvents.