This study investigates the influence of microwave irradiation on coal composition, pore structure, coal rank, and combustion characteristics of typical brown coals in China. Results show that the upgrading process significantly decreased the inherent moisture, and increased calorific value and fixed carbon content. After upgrading, pore distribution extended to micropore region, oxygen functional groups were reduced and destroyed, and the apparent aromaticity increased suggesting an improvement in the coal rank. Based on thermogravimetric analysis, the combustion processes of upgraded coals were delayed toward the high temperature region, and the temperatures of ignition, peak and burnout increased. Based on the average combustion rate and comprehensive combustion parameter, the upgraded coals performed better compared with raw brown coals and a high rank coal. In ignition and burnout segments, the activation energy increased but exhibited a decrease in the combustion stage.