The emerging solar interfacial evaporation (SIE) technology is an effective measure to address freshwater resources. An efficient and stable solar interfacial evaporator cannot be achieved without the synergy of three key factors: water transport, solar thermal conversion and thermal management. The performance of a solar interfacial evaporator can be improved through the rational selection of materials and the structural design of these three key factors. Due to superior nanostructures, electrospun nanofibrous materials often exhibit some unique properties that facilitate the construction of solar interface evaporators with good performance. So far, electrospinning has been used to prepare structures such as solar absorbers, water transportation and thermal insulation in various solar interfacial evaporators. This review presents the fundamental research and technological development in the application of electrospinning techniques to solar interfacial evaporators on structures, morphology and properties. Then we summary the latest advances in the use of electrospinning technology in solar interfacial evaporators and present the current issues facing the application of electrospinning technology to solar interfacial evaporators. These systematic discussions can provide ideas and approaches for the rational design of electrospun nanofiber materials for solar interfacial evaporators in the future.