<p>Biomass, as a renewable and environmentally friendly energy source, has attracted widespread attention in recent years. Among biomass-derived platform molecules, 5-hydroxymethylfurfural (HMF) is particularly important due to its potential to be converted into a variety of high-value chemicals. The development of green and efficient catalysts is crucial for the selective conversion of HMF. In this study, industrial solid waste coal fly ash (CFA) was utilized as a support to prepare a series of iron–nickel bimetallic catalysts via a simple grinding method for the catalytic hydrogenolysis of HMF to biofuel 2,5-dimethylfuran (DMF), a promising biofuel. The structural and surface properties of the catalysts were characterized by XRD, TG, XPS, and TEM. The effects of Fe–Ni composition, reaction temperature, catalyst dosage, and reaction time on HMF conversion and DMF selectivity were systematically investigated. The results revealed that the optimized catalyst achieved complete conversion of HMF and a DMF selectivity of up to 97.4% under mild conditions. Furthermore, the incorporation of Fe significantly enhanced the hydrogenation selectivity of Ni, demonstrating a strong synergistic effect in the bimetallic system. This work provides a sustainable approach for biomass valorization and highlights the potential of repurposing industrial waste materials for catalytic applications.</p> Graphical Abstract <p></p>