The times at which devolatilising coal particles fragmented were compared with their devolatilisation times in a fluidized bed combustor. Whereas the devolatilisation times were similar, the time to first fragmentation varied markedly from coat to coal. Immediate fragmentation was attributed to thermal shock. Fragmentation during the first 1/3 of the devolatilisation time was attributed to the internal pressure generated from restricted transport of volatiles through the pores in the coal structure. Fragmentation near the end of devolatilisation may occur due to weakening of the coal structure by loss of volatiles. Primary fragmentation did not affect the devolatilisation time, even for coals which fragmented early in their devolatilisation time.