The development of active and low-cost transition metal oxide-based catalysts was vital for the catalytic oxidation of toluene. This study aimed to prepare Fe-Mn oxide catalysts by Mn-rich limonite, and investigate the catalytic activity and mechanism for toluene oxidation. The natural Mn-rich limonite was thermally activated at different temperatures and these thermally activated samples exhibited different oxidation activities. YL-300, obtained through thermal treatment at 300°C, exhibited excellent catalytic activity, showing 90% toluene conversion at 239°C (1000 ppm toluene) and remarkable catalytic stability even in the presence of water vapor (5 vol.%). The amount of oxygen vacancies in the catalyst was regulated by tuning the thermal treatment temperatures. Optimal thermal treatment facilitated the increase of oxygen vacancies and enhanced the oxygen mobility and redox capacity of YL-300, contributing to the complete oxidation of toluene to H2O and CO2. The oxidation of toluene was greatly influenced by the adsorbed oxygen species. This study demonstrates the potential of Mn-rich limonite as a promising catalyst for toluene oxidation, thereby promoting the utilization of natural mineral materials in the field of environmental pollution control.