Composite membranes with asymmetric traits have gained attention in liquid separation, featuring gradient chemical and physical attributes that align or oppose mass transfer direction. Chemically asymmetric configurations harness internal driving forces to heighten separation efficiency, rendering them an appealing option for heightened separation efficiency and fouling prevention. Concurrently, the internal hierarchical structure differences within composite membranes—such as fiber‐based structural adjustments and the gradient density of functional layers—yield the dual benefits of effective liquid repelling and heightened transport efficiency. Unlike conventional phase‐change methods, electrospinning technology possesses advantages in constructing and governing composite fibrous membrane materials with asymmetric chemistry and hierarchical structures, driven by its adaptable stacking methodologies. Notably, the inherent pore structure of electrospun nanofibrous membranes emerges as a proven solution for minimizing transport resistance. In recent times, interest has surged in electrospun nanofibrous membranes endowed with internal asymmetric properties. However, the spotlight has predominantly graced Janus membranes, spotlighting opposite wettability on different sides, leaving other facets of asymmetric membrane enhancement somewhat underexplored. This comprehensive work unveils recent strides in design, fabrication, facilitated transport mechanisms, and real‐world liquid separation applications, all under the aegis of electrospun nanofiber membranes, each endowed with distinct asymmetric properties.