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Facile fabrication of porous carbon materials from waste halogenated plastic is highly attractive but frequently hampered due to potential release of halogenated organic pollutants. In this study, a novel type of carbon hybrid was tentatively synthesized from a real-world halogenated plastic as an inexpensive carbon source by sub/supercritical carbon dioxide carbonization technique. It was found that halogen-free carbon carrier was advantageously synthesized through carbonization of halogenated plastic without using catalysts due to zip depolymerization, random chain cracking and free radical reactions induced by sub/supercritical carbon dioxide technique. Exhibiting with more abundant functional groups including C–O, C O groups than pyrolytic carbon carrier, the derived carbon carrier demonstrated excellent performance in selective recovery of lithium from cathode powder with highest recovery efficiency of 93.6%. Mechanism study indicated that cathode powder was transformed into low-valence states of transition metals/metal oxides and released lithium as lithium carbonate due to collapse of oxygen framework via carbothermic reduction. This work provides an applicable and green process for synthesis of alternative carbon carrier from waste halogenated plastic and its application as carbothermic reductant in lithium recovery. • Halogen-free carbothermic hybrid was synthesized from halogenated plastic by Sc-CO 2. • Adequate dehalogenation and carbonization was achieved with no presence of catalyst. • Hybrid favored lithium recovery due to synergistic effect between rich active groups. • Transition metals were converted to low-valence state after carbothermic treatment. • Lithium was released as Li 2 CO 3 due to oxygen framework of cathode material collapse. [ABSTRACT FROM AUTHOR]