The fracture toughness of white cast irons is related to the morphology of eutectic carbides,being better when isolated than when network-like. In this paper observations on the breakup of eutectic cementite network during annealing treatment of white cast irons are reported using a high temperature microscope and scanning electron microscopy (SEM). Dissolution-induced breakup and capillarity-induced breakup are identified. The former occurs through growth of holes and pre-existing fissures as well as through fragmentation at narrow necks and narrow roots of branches. The latter is observed through growth of perturbations. Dissolution-induced breakup is closely associated with the morphology of the as-cast eutectic cementite. A combination of solidification processing and heat treatment thus produces a more positive breakup effect.