The devolatilization process has important influence on the formation of PM10 (particulate matter with an aerodynamic diameter of <= 10.0 mu m) in oxy-fuel combustion of pulverized coal but has been explored little. A bituminous coal was devolatilized in either CO2 or N-2 at 1573 K on a drop-tube furnace (DTF) to produce CO2-char and N-2-char. Coal and its char samples were burned at 1573 K and in 29 vol % O-2/71 vol % CO2. PM10 was collected and segregated into 13 size fractions, which were subjected to subsequent analysis. The results show that the particle mass size distributions of PM10 from coal and chars have similar peak and trough sizes, suggesting that the devolatilization process has insignificant influence on the major pathways of PM10, formation. Three particle modes can be identified, i.e., ultrafine mode (<0.5 mu m, PM0.5), central mode (0.5-2.5 mu m, PM0.5-2.5), and coarse mode (2.5-10 mu m, PM2.5-10). Coal combustion produces more PM PM0.5-2.5 than char combustion, suggesting that the devolatilization process has important influence on the production of PM0.5 and PM0.5-2.5. In contrast, the PM2.5-10 yield is insignificantly affected by the devolatilization process under the investigated conditions. In addition, the combustion of CO2-char generates more PM0.5 and PM0.5-2.5 than that of N-2-char, indicating that the devolatilization in CO2 favors the formation of PM0.5 and PM0.5-2.5.