Exploring combinatorial materials, as well as rational device configuration design, are assumed to be the key strategies for deploying versatile electrochemical devices. MXene sheets have revealed a high hydrophilic surface with proper mechanical and electrical characteristics, rendering them supreme additive candidates to integrate in electrospun electrochemical power tools. The synergetic effects of MXene 2D layers with the nanofibrous networks can boost actuator responsive ability, battery capacity retention, fuel cell stability, sensor sensitivity, and supercapacitor areal capacitance. Their superior mechanical features can be endowed to the electrospun layers through the embedding of the MXene additive. In this review, the preparation and inherent features of the MXene configurations are briefly evaluated. The fabrication and overall performance of the MXene‐loaded nanofibers applicable in electrochemical actuators, batteries, fuel cells, sensors, and supercapacitors are comprehensively figured out. Eventually, an outlook on the future development of MXene‐based electrospun composites is presented. A substantial focus has been devoted to date to engineering conjugated MXene and electrospun fibrous frames. The potential performance of the MXene‐decorated nanofibers presents a bright future of nanoengineering toward technological growth. Meanwhile, a balance between the pros and cons of the synthesized MXene composite layers is worthwhile to consider in the future.