The review article published in Industrial Chemistry & Materials explores chemical-assisted water electrolysis as an innovative method for green hydrogen (H2) production. The research aims to provide a sustainable and efficient alternative to conventional techniques, crucial for addressing the increasing global demand for cleaner energy sources and reducing carbon dioxide emissions. Advancements in H2 production technologies are highlighted, emphasizing the importance of hydrogen as a zero-emission combustion option with a high energy density. Among these technologies, H2O electrolysis emerges as a key process for producing green hydrogen, but challenges like high reaction overpotentials necessitate innovative approaches. The study delves into the novel approach of chemical-assisted electrolysis, which involves alternative oxidation reactions to enhance H2 production efficiency and reduce pollutants. Various chemical reactions like alcohol, ammonia, urea, hydrazine, and biomass oxidation are explored for their unique advantages and challenges, focusing on lowering voltages and improving production efficiency. The findings demonstrate that chemical-assisted electrolysis significantly enhances H2 production efficiency by lowering voltages, with different reactions offering diverse benefits and facing specific challenges. The applications of this technology extend to industries beyond hydrogen production, such as wastewater treatment and renewable energy storage, promoting resource recovery and pollution mitigation. The review concludes by underlining the importance of advancing catalyst design, optimizing reaction conditions, and scaling up these technologies for industrial applications. Future work is encouraged to overcome challenges in stability, current density, and cost-effectiveness to drive global decarbonization and establish a sustainable energy economy.