Ceramic yield, density, volume change and pore size distribution were measured for radiation- and thermally cured PCS powder when they were pyrolyzed in the temperature range of 673–973 K. Higher ceramic yield was obtained for radiation-cured powder due to smaller amount of evolved gas. Temperature dependence of volume change and the total pore volume show that the formation and disappearance of pores in the powders were determined by the volume shrinkage and evolution of decomposed gases. Volume shrinkage narrowed the pore size distribution for radiation-cured powder. For thermally cured powder, the narrowing of size distribution was disturbed by aggregated pores. Smaller amount of evolved gas from radiation-cured powder relative to thermally cured powder prevented the aggregation of pores and provided the narrow size distribution.