Since the introduction of the concept of single-atom (SA) catalysis, numerous SA catalysts (SACs) with exceptional catalytic performance have been developed. Electrospinning represents a powerful technique for fabricating nanofibrous materials, characterized by high porosity, distinct electron/mass transfer property, self-supporting capability, and low density. Consequently, integrating SACs with electrospun nanofibers (ENFs) harnesses their structural advantages, thereby augmenting catalytic efficacy. This review examines the concept of SA-ENFs, underscoring the synergy between the nano-sized support architecture and atomic-level catalysts, which collectively offer abundant catalytic active sites. Furthermore, the well-defined spatial arrangement of nanofibers combined with highly efficient SAs imparts unique electron transfer and electrolyte transport capabilities, thereby promoting the catalytic performance. Herein, a detailed understanding of the influence of the coordination environment, and the interactions between multiple active sites within ENFs on the electrocatalytic performance is highlighted. This review also identifies potential challenges facing this novel class of SA-ENFs in electrocatalytic applications.
