Abstract: Activated carbon suffers from severe performance deterioration during the adsorption of reactive volatile organic compounds (VOCs), such as styrene, due to the accumulation of irreversible deposits within its pore structure. In this study, an extruded coal-based activated carbon was prepared from Jilangde long-flame coal (Hami, Xinjiang, China) using high-temperature coal tar as a binder through extrusion molding, carbonization, and steam activation. The effects of coal-to-tar ratio, pre-oxidation, carbonization, and activation conditions on the structural properties and styrene adsorption–desorption performances of the activated carbon were systematically investigated. Results showed that a coal powder-to-coal tar mass ratio of 72:28 derived extruded cylinders with a dense structure and smooth external surface. Pre-oxidation induced the formation of a three-dimensional cross-linked network, resulting in chars with short-range ordered and long-range disordered microcrystalline structures. Increasing the steam activation temperature and duration significantly enhanced the specific surface area, total pore volume, and mesopore proportion, leading to the development of a hierarchical pore structure. Among the activated carbon samples, AC-880-180 exhibited the highest specific surface area of 1366 m2/g and a mesopore ratio exceeding 43%. Styrene adsorption–desorption cycling tests demonstrated that AC-880-180, possessing a high mesopore content, achieved a superior adsorption capacity (784 mg/g) and a higher first-cycle desorption efficiency (85.08%), while exhibiting negligible deposit accumulation in the following cycles. These findings indicate that appropriately designed pre-oxidation and activation processes can effectively tailor the hierarchical pore structure of coal-based activated carbon, thereby enhancing styrene desorption efficiency and regeneration stability. This work provides an effective strategy for the development of dedicated adsorbents for the pollution control of reactive VOC emissions.