Inspired by the self-cleaning phenomenon in nature biology, superwettable materials systems have been increasingly studied by multidisciplinary scientists in past two decades. Among various fabrication methods, electrospinning technology, with superior capability of comprehensive coordination of surface chemical composition and hierarchical micro/nanostructures, has been proved to be a versatile method to fabricate diverse fibrous materials with superwettability from polymers, ceramics, to composites. This review first introduces the progress of electrospinning technology in generating various hierarchical structured nanofibers. Then, the wetting theory of liquid on fibers and recent approaches toward fabricating bioinspired electrospun micro/nanofibers with superwettability are described. Based on the special wettability to different liquids, the electrospun nanofibrous materials play significant roles in liquid mixtures separations, water collection, unidirectional liquid penetrations, and in environmentally responsive materials. Finally, the challenges and promising prospects on electrospun superwettability nanofibrous materials are highlighted.