Electric signals exert critical roles in tissue regeneration. Electrotherapeutic devices in the clinic have confirmed clinical effectiveness, but they may cause low patient compliance and infection risks due to invasive electrodes and external power sources. Through electrospinning, electroactive electrospun scaffolds address these shortcomings. This review first outlines the physiological cues of electric signals in electrosensitive tissue regeneration and signaling pathways induced by electric stimulations for tissue regeneration. Next, it details basic fabrications for extracellular matrix mimetic scaffolds, emphasizing the endowment of surface potential by voltage polarity and the selection of electrospinning methods and materials. Then, it critically analyzes methodologies to imbue scaffolds with electroconductivity to facilitate cell-to-cell signaling and piezoelectric effects or triboelectrification to form electrical cues for tissue regeneration. Moreover, smart applications of electroactive electrospun scaffolds for mimicking bioelectric niches are summarized, including conductive or piezoelectric electrospun scaffolds, electroactive composite implants, self-powered nanogenerators, and smart electroactive drug delivery devices. Finally, current challenges and future directions toward clinical implementation are discussed.