One-dimensional (1D) SiO₂ nanofibers (SNFs), one of the most popular inorganic nanomaterials, have aroused widespread attention because of their excellent chemical stability, as well as unique optical and thermal characteristics. Electrospinning is a straightforward and versatile method to prepare 1D SNFs with programmable structures, manageable dimensions, and modifiable properties, which hold great potential in many cutting-edge applications including aerospace, nanodevice, and energy. In this review, substantial advances in the structural design, controllable synthesis, and multifunctional applications of electrospun SNFs are highlighted. We begin with a brief introduction to the fundamental principles, available raw materials, and typical apparatus of electrospun SNFs. We then discuss the strategies for preparing SNFs with diverse structures in detail, especially stressing the newly emerging three-dimensional SiO₂ nanofibrous aerogels. We continue with focus on major breakthroughs about brittleness-to-flexibility transition of SNFs and the means to achieve their mechanical reinforcement. In addition, we showcase recent applications enabled by electrospun SNFs, with particular emphasis on physical protection, health care and water treatment. In the end, we summarize this review and provide some perspectives on the future development direction of electrospun SNFs.