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A composite, three-layered membrane for membrane distillation was prepared from electrospun polyvinylidene fluoride (PVDF) nanofibers supported by commercial polyethersulfone (PES) nanofiber based nonwoven from E.I. duPont de Nemours company (DuPont). The membranes were tested in direct contact membrane distillation (DCMD) using a 5.0 M sodium chloride brine as a feed solution. The triple layer membrane combines the hydrophobicity of PVDF and the robustness of the PES. The triple layer membrane demonstrated excellent performance in DCMD (i.e., relatively high water flux compared to the commercial PVDF membrane and a complete salt rejection of the brine) with mechanical properties imparted by the PES layer. This work is the first to demonstrate the use of a commercially produced nanofiber nonwoven for membrane distillation.