The conversion of waste tire pyrolysis oil (WTPO) into S‐doped porous carbon nanorods (labeled as WPCNs) with hierarchical pore structure is realized by a simple template‐directed approach. The specific surface area of as‐obtained porous carbon nanorods can reach up to 1448 m2 g−1 without the addition of any activating agent. As the capacitive electrode, WPCNs possess the extraordinary compatibility to capacitance, different electrolyte systems as well as long‐term cycle life even at a commercial‐level areal mass loading (10 mg cm−2). Besides, only an extremely small capacitance fluctuation is observed under the extreme circumstance (−40 to 80 °C), reflecting the excellent high‐ and low‐temperature performance. The relationship between the pore structure and capacitive behavior is analyzed by comparing WPCNs with mesopores‐dominated asphalt‐derived porous carbon nanorods (APCNs) and micropores‐dominated activated carbon. The molecular dynamics simulation further reveals the ion diffusion and transfer ability of the as‐prepared carbon materials under different pore size distribution. The total ion flow (NT) of WPCNs calculated by the simulation is obviously larger than APCNs and the NT ratio between them is similar with the experimental average capacitance ratio. Furthermore, this work also provides a valuable strategy to prepare the electrode material with high capacitive energy storage ability through the high value‐added utilization of WTPO.
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