Photothermal interfacial evaporation with low cost and environmental friendliness has attracted much attention. However, there are still many problems with this technology, such as heat loss and salt accumulation. Due to their different structures and adjustable chemical composition, electrospun nanofiber materials generally exhibit some unique properties that provide new approaches to address the aforementioned issues. In this review, the rational design principles for improving the total efficiency of solar evaporation are described for thermal/water management systems and salt-resistance strategies. And we review the state-of-the-art advancements in photothermal evaporation based on nanofiber materials and discuss their derivative applications in desalination, water purification, and power generation. Finally, we highlight key challenges and opportunities in both fundamental research and practical applications to inform further developments in the field of interfacial evaporation.