ABSTRACT Modifying the content of oxygen vacancies (OVs) has emerged as a crucial approach to tailoring silicate's adsorption properties, microstructure, conductivity, and catalytic performance. Some studies have reported the formation of OVs during ammonia treatment. However, there are limited studies on the production of OV-enriched mullite by treating it with N-containing compounds at low temperatures. In this work, formamide, urea, and ammonium acetate were used as ammonia-assisted reduction modifiers to induce oxygen vacancies in mullite at 30 ℃, 60 ℃, and 90 °C. The aim was to enhance the enrichment effect of heavy metals (Cr, Cu, Mn, Ni, Pb, Zn) during the co-combustion of coal and biomass. The modified mullite was analyzed by using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area analysis, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The results indicated that the particle size of mullite decreased, and the concentration of internal Al3+ ions and oxygen vacancies was enhanced. Coal-biomass-mullite combustion experiments were conducted in a tubular furnace at 900 °C, revealing a significant enhancement in the enrichment of heavy metals during the combustion process, particularly when the modification temperature was 60 °C using ammonium acetate as the modifier. This work holds significant importance for developing novel heavy metal adsorbents and the reduction of pollutant emissions from coal-biomass co-combustion in industrial applications.