Surface and interface engineering of catalysts from atomic level to macroscale exhibit good performance in regulating conversion, selectivity, and stability. Electrospinning offers such multiscale flexibility in tuning surface and interface structures and compositions for the design of fiber catalysts. This review presents an overview on the surface and interface engineering of electrospun nanofibers for heterogeneous catalysts designing. First, the building strategies for regulating catalytic performance on surface and interface at different scales are introduced. Then, typical research achievements of surface and interface regulation strategies of nanofiber catalysts in different scales are summarized, including atomic vacancy and doping at microscale, heterojunction interfaces at mesoscale, and surfaces/interfaces with special wettability at macroscale. The typical catalytic reactions are introduced that involve classical small molecule hydrogenation, oxygen evolution reaction, and pollutant photocatalytic degradation, as well as the recently emerging CO