Abstract: Plastic waste is both a critical pollution problem and a promising resource for low-carbon hydrogen. This review summarizes thermochemical and emerging routes for H2 production from plastic waste, focusing on pyrolysis-integrated methods, i.e., pyrolysis catalytic steam reforming (PCSR), pyrolysis catalytic dry reforming (PCDR), pyrolysis catalytic oxidative steam reforming (PCOSR), pyrolysis plasma catalytic reforming (PPCR), and microwave-assisted pyrolysis (MAP), alongside photo-reforming (PR), electro-reforming (ER), and flash Joule heating (FJH). The different alternatives were compared in terms of H2 yields, gas compositions, and the influence of operating variables such as temperature, catalysts, and feed characteristics. Moreover, the subsequent H2 purification via pressure swing adsorption (PSA) and membranes is also assessed. Among reported systems, PCSR and PCDR show the highest and most scalable H2 production, with pilot-scale demonstrations, while PR and ER provide high-purity H2 under mild conditions but remain limited in throughput. Remaining challenges include catalyst deactivation, energy and carbon efficiency, process integration, and techno-economic feasibility, which must be addressed to enable large-scale deployment of plastic-to-hydrogen technologies within a circular H2 economy.

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