In order to reduce overall fuel consumption, or partially substitute a "valuable" fuel with a poor one, in electric power plant boilers, oxygen enrichment of combustion air can be very effective. Combustion characteristics of three Chinese pulverized coals, Shenmu bituminous, Tianhushan anthracite, and Duolun lignite, and three different particle sizes, under high oxygen concentrations more than 21%, have been investigated using thermogravimetric/differential scanning calorimetry analysis (TG/DSC) and a drop-tube furnace. Results showed that the ignitability, the combustion property, and the burnout were largely improved when added oxygen was used, especially for small particles, the influence of oxygen on the bituminous coal was greater than the lignite and the anthracite, and the suitable O-2 concentration for the ignition of pulverized coal flow should be controlled below 40%.