The design of composite materials leads to the development of multi-component systems where each constituent has a specific function in the material, from technological and/or application points of view. Examples of such composite systems are the cordierite-mullite refractory materials investigated in this contribution. Two different commercially available compositions were selected for evaluation of the influence of microstructure on fracture behaviour under thermal shock conditions. The materials were exposed to water-quench tests from 1250°C and subsequently the fracture toughness was evaluated using the chevron notched specimen technique. The results were compared to those obtained on as-received materials. Microstructural damage was also studied applying fractographic techniques with the aim to gain knowledge on the thermal shock damage mechanisms acting in the materials.