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Growing global energy demand and the imperative to reduce greenhouse gas emissions have accelerated interest in low-carbon hydrogen production. This review synthesizes advances at the intersection of electrolysis and biomass pyrolysis, with particular emphasis on the emerging role of biochar as a functional and catalytic material that enhances hydrogen generation while supporting sustainable bioenergy value chains. Recent evidence shows that biochar-assisted water electrolysis (BAWE) can lower energy requirements, improve reaction efficiency, and valorize locally available biomass resources. This positions biochar as a promising complement to conventional green hydrogen pathways. The review further assesses South Africa’s evolving policy and regulatory architecture by highlighting the country’s ambition to build a competitive hydrogen economy alongside structural constraints such as limited electrolyzer manufacturing capability, inadequate infrastructure, and insufficiently targeted frameworks for technology scale-up. The review analysis therefore emphasizes that integrating biomass-derived materials into hydrogen production presents an underexplored yet high-potential route for advancing national decarbonization goals. Strengthened research, development, and innovation systems, supported by coherent and technology-specific policy measures, will be essential for South Africa to unlock the full economic, environmental, and industrial benefits of a green hydrogen and biochar-integrated future. Full article