Abstract: Coal liquefaction pitch （CLP）, characterized by its unique graphite-like microcrystalline structure and high carbon content, is considered a potential precursor for the preparation of high-performance activated carbon fibers （ACFs） for energy storage applications. Utilizing CLP as a feedstock offers significant economic advantages, enabling not only a high carbon yield during carbonization but also the preservation of a well-developed crystalline structure and superior electrical conductivity. Nevertheless, critical challenges remain in optimizing CLP-based ACFs: the lack of clear optimization strategies for the CO₂ activation process and the insufficient study of its correlation with electrochemical performance. To address this, CLP-derived ACFs were prepared via CO₂ activation, and the effects of activation temperature and soaking time on chemical composition, surface functional groups, pore structure, and electrochemical performance were systematically investigated. The results show that effective micropore development and pore expansion occur predominantly at temperatures above 900 ℃, where CO₂ preferentially reacts at defect sites within the carbon framework. Soaking time emerges as a pivotal factor governing pore structural evolution. While prolonged activation enhances specific surface area, it simultaneously reduces micropore volume fraction and broadens the average pore size due to micropore coalescence into mesopores. Through optimization, the ACFs-950-3.0 sample achieved a balanced porous structure with a high specific surface area of 2 369.614  m²/g, a microporosity volume fraction of 91.6%, and an average pore diameter of 1.87 nm. Electrochemical evaluation demonstrates that ACFs-950-3.0 sample delivers a specific capacitance of 315  F/g at a current density of 1 A/g and retains 98.9% of its initial capacitance after 10 000 charge–discharge cycles, demonstrating outstanding double-layer capacitive behavior and exceptional cycling stability. These findings provide essential insights and technical guidance for the high-value utilization of CLP and its advancement in energy storage technologies.