<p>Porous carbon fibers possess the advantages of high conductivity, rich channels for mass transport and electron transfer, and abundant anchoring sites for loading highly active components. These favorable merits enable porous carbon fibers to be promising candidates for serving as advanced electrocatalysts. To gain a deeper understanding of the merits and potentials of porous carbon fibers for boosting electrocatalytic reactions, this review summarizes recent advances in modifying them to boost electrocatalytic reactions. The review is started by discussing the typical synthesis methods of porous carbon fibers, which include the electrospinning-carbonization, in-situ composite growth, and chemical etching methods. Subsequently, some effective strategies for the modification of porous carbon fibers are also discussed, such as heteroatom doping, defect engineering, single-metal and their compounds doping, and coupling with other compounds. Moreover, the applications of porous carbon fibers for boosting electrocatalytic reactions (e.g., ORR, OER, HER, CO₂ reduction, nitrate reduction) are also comprehensively discussed, highlighting the significance of porous carbon fibers for boosting electrocatalytic reactions. Finally, the review also lists some challenges of this interesting field and proposes the direction for guiding the synthesis of more efficient electrocatalysts.</p>