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Membrane distillation (MD) is an emerging technology for water recovery from hypersaline wastewater. Membrane scaling and wetting are the drawbacks that prevent the widespread implementation of the MD process. In this study, coaxially electrospun polyvinylidene fluoride-co-hexafluoropropylene (PVDF-co-HFP) nanofibrous membranes were fabricated with re-entrant architecture and enhanced hydrophobicity/omniphobicity. The multiscale roughness was constructed by incorporating Al2O3 nanoparticles and 1H, 1H, 2H, 2H Perfluorodecyltriethoxysilane in the sheath solution. High resolution transmission electron microscopy (HR-TEM) could confirm the formation of the core-sheath nanofibrous membranes, which exhibited a water contact angle of ~142.5° and enhanced surface roughness. The membrane displayed a stable vapor flux of 12 L.m−2.h−1 (LMH) for a 7.0 wt.% NaCl feed solution and no loss in permeate quality or quantity. Long-term water recovery from 10.5 wt.% NaCl feed solution was determined to be 8–10 LMH with >99.9% NaCl rejection for up to 5 cycles of operation (60 h). The membranes exhibited excellent resistance to wetting even above the critical micelle concentration (CMC) for surfactants in the order sodium dodecyl sulphate (SDS) (16 mM) > cetyltrimethylammonium bromide (CTAB) (1.5 mM) > Tween 80 (0.10 mM). The presence of salts further deteriorated membrane performance for SDS (12 mM) and Tween-80 (0.05 mM). These coaxial electrospun nanofibrous membranes are robust and can be explored for long-term applications. [ABSTRACT FROM AUTHOR]