This article is concerned with the overview of the activated carbon fibers. Firstly, this review provides a comprehensive survey of the overall processes for the synthesis of the activated carbon fibers from the carbonaceous materials. Subsequently, the physicochemical properties such as pore structures and surface oxygen functional groups of the activated carbon fibers were discussed in detail. Finally, as electrochemical applications of the activated carbon fibers to electrode materials for electric double-layer capacitor (EDLC), the electrochemical characteristics of the activated carbon fiber electrodes and the various methods to improve the capacitance and rate capability were introduced. In particular, the effect of pore length distribution (PLD) on kinetics of double-layer charging/discharging was discussed based upon the experimental and theoretical results in our work. And then we discussed in detail the applications of the activated carbon fibers to adsorbent materials for purification of liquid and gas.