Abstract: Carbon materials are widely recognized as highly promising electrode materials for various energy storage system applications. Coal tar residues (CTR), as a type of carbon-rich solid waste with high value-added utilization, are crucially important for the development of a more sustainable world. In this study, we employed a straightforward direct carbonization method within the temperature range of 700–1000°C to convert the worthless solid waste CTR into economically valuable carbon materials as anodes for potassium-ion batteries (PIBs). The effect of carbonization temperature on the microstructure and the potassium ions storage properties of CTR-derived carbons (CTRCs) were systematically explored by structural and morphological characterization, alongside electrochemical performances assessment. Based on the co-regulation between the turbine layers, crystal structure, pore structure, functional groups, and electrical conductivity of CTR-derived carbon carbonized at 900°C (CTRC-900_H), the electrode material with high reversible capacity of 265.6 mAh·g⁻¹ at 50 mA·g⁻¹, a desirable cycling stability with 93.8% capacity retention even after 100 cycles, and the remarkable rate performance for PIBs were obtained. Furthermore, cyclic voltammetry (CV) at different scan rates and galvanostatic intermittent titration technique (GITT) have been employed to explore the potassium ions storage mechanism and electrochemical kinetics of CTRCs. Results indicate that the electrode behavior is predominantly governed by surface-induced capacitive processes, particularly under high current densities, with the potassium storage mechanism characterized by an “adsorption–weak intercalation” mechanism. This work highlights the potential of CTR-based carbon as a promising electrode material category suitable for high-performance PIBs electrodes, while also provides valuable insights into the new avenues for the high value-added utilization of CTR.