The electrochemical reduction of CO2 (CO2RR) into valuable products represents a step towards alleviating global warming and the energy crisis. However, the sluggish kinetics of the CO2RR and the competitive hydrogen evolution reaction (HER) still limit the application of CO2RR. In order to solve these problems, catalysts that can reduce CO2 with high activity, selectivity and stability are required. Recently, electrospun nanofibers have attracted particular interest as CO2RR catalysts due to their high conductivity, large surface area, superior stability, etc. In this review, we briefly introduce electrospinning technology and the fundamentals of the CO2RR. Then, the recent progress of CO2RR catalysts prepared through electrospinning, including heteroatom-doped and metal-decorated carbon materials and metal fiber materials are systematically discussed. Finally, the future perspectives and challenges of electrospun materials for CO2RR are presented. This mini review is anticipated to inspire better understanding and further development of electrospun materials for promoting CO2 electrolysis.