AbstractSolid‐state electrolytes (SSEs), being the key component of solid‐state lithium batteries, have a significant impact on battery performance. Rational materials structure and composition engineering on SSEs are promising to improve their Li+ conductivity, interfacial contact, and mechanical integrity. Among the fabrication approaches, the electrospinning technique has attracted tremendous attention due to its own merits in constructing a three‐dimensional framework of SSEs with precise porosity structure, tunable materials composition, easy operation, and superior physicochemical properties. To this end, in this review, we provide a comprehensive summary of the recent development of electrospinning techniques for high‐performance SSEs. Firstly, we introduce the historical development of SSEs and summarize the fundamentals, including the Li+ transport mechanism and materials selection principle. Then, the versatility of electrospinning technologies in the construction of the three main types of SSEs and stabilization of lithium metal anodes is comprehensively discussed. Finally, a perspective on future research directions based on previous work is highlighted for developing high‐performance solid‐state lithium batteries based on electrospinning techniques.