Amidst growing global concerns for environmental sustainability and the urgent need for renewable energy sources, this research delves into alternative energy solutions using agricultural byproducts. It specifically focuses on utilizing agroforestry waste as a key component in the development of efficient and eco-friendly energy conversion technologies. The study systematically investigates the co-gasification of agroforestry waste with coal, aiming to optimize structure to significantly enhance energy conversion efficiency. The structural evolution of char and its impact on gasification performance was studied by blending agroforestry waste from lily leaves (LIL) with Yuxi coal (YXC) at different ratios. The experiments reveal that the blend ratio (3:1) significantly enhances the gasification reactivity of YXC. At a temperature of 1000 °C, the reactivity index, R0.9, was found to be 2.59 times greater than that of YXC alone, indicating a substantial improvement in reactivity. This enhanced reactivity is attributed to notable alterations in the microstructure and pore distribution within the blended char. This blended char exhibited a higher prevalence of disordered structures and more volatile functional groups (C–O and CC) and phases enhance the complexity of catalytic actions, facilitating gasification reactions. This research underscores the potential of integrating agroforestry waste into energy production systems as a sustainable solution that optimizes energy conversion processes and contributes to environmental preservation, aligns with the global pursuit of eco-friendly energy alternatives.