The study investigates hydrogen production from agricultural woven bags (AWB) and corncobs (CC) through co-gasification over NiX-Ca2Fe2O5 catalysts. The research aims to optimize hydrogen efficiency and suppress tar formation. Results show synergistic effects at 750°C with a 66% AWB blending ratio, enhancing syngas yield and H2 production. Steam as a gasifying agent promotes tar reforming, leading to high H2 production. The Ni–Fe–Ca/perovskite-type catalyst with 15 wt% nickel doping demonstrates optimal performance, improving H2 production and reducing methane content. This study highlights the potential of waste biomass and plastic co-gasification for sustainable hydrogen production, emphasizing the importance of perovskite catalysts in enhancing hydrogen selectivity and reducing carbon deposition.