<p>The catalytic co-pyrolysis of agricultural and plastic wastes represents a promising strategy for advancing circular bioeconomy by converting waste into valuable products. This study introduces iron tailing-derived catalysts, denoted as TT1, for the synergistic co-processing of wheat straw and polyethylene, enabling the simultaneous production of bio-oil and hydrogen-rich syngas. At the optimal 50% polyethylene (PE) ratio, TT1 drives a cascade mechanism where Fe⁰/Fe²⁺ catalyze dehydrogenation and β-scission reactions, leading to a 29-fold enhancement in hydrogen yield, reaching 863.01&#xa0;mL/g compared to non-catalytic pyrolysis. This process also achieves a 74.9% reduction in CO₂ emissions and boosts the selectivity for medium-chain hydrocarbons (C_12–20) to 64.11%. The transfer of hydrogen radicals from plastics significantly mitigates carbon deposition. Life cycle assessment (LCA) demonstrates that this co-processing technology achieves a significant net negative carbon footprint of –0.897&#xa0;kg CO₂ eq, delivering nearly twice the emission reduction benefit of traditional resource recovery processes and highlighting its outstanding potential for climate change mitigation. This work lays the foundation for a sustainable “waste-to-wealth” paradigm, offering a scalable solution for concurrent resource recovery and renewable energy production.</p> Graphical Abstract <p></p>