This study pioneers the application of metal-doped Fe-Al as multifunctional redox catalysts for tunable syngas production from plastics via a microwave-assisted process (CLG). We rationally designed a series of redox catalysts (Ni, Ca, Ce, Sr, Co) to unlock efficient H₂-rich syngas production from (high-density polyethylene) HDPE. A class of metal-doping (Ni, Ca, Ce, Sr, and Co) Fe-Al redox catalysts was engineered, with Ni-doped Fe-Al (Ni-Fe-Al) exhibiting the excellent H₂-rich syngas production (75.32 mmol/gHDPE syngas, 47.09 mmol/gHDPE H₂). This is attributed to the improved redox activity, which facilitates efficient lattice oxygen transfer and catalytic reforming reactions, alongside improved microwave absorption and a porous structure that promotes reactant access. This strategic material design, coupled with process parameter optimization (800 W, redox catalyst/plastic = 2.0), developed a highly efficient HDPE-to-syngas conversion system. The process produced a high-quality syngas (90.03% H₂ + CO, H₂/CO ratio = 2.27) with a rapid heating rate (233.0 °C/min) and minimal energy input (3.52 kWh/molgas). This work provides not just an effective upcycling route for plastics, but a fundamental blueprint for designing advanced redox catalysts to unlock the full potential of microwave-CLG.