High-performance mullite-based composite ceramics were prepared successfully using natural kaolin and alumina as raw materials and ZrO2 as an additive. The influence of sintering temperature and ZrO2 content on the sintering behaviour and mechanical properties of zirconia-toughened mullite ceramics was studied systematically. With increasing sintering temperature from 1450°C to 1560°C, the primary phases of as-sintered composite ceramics were mullite and corundum with a small amount of ZrO2, and the bulk density of the composite ceramics increased from 2.29 to 2.72 g cm–3. Furthermore, the ZrO2 phase transition promoted transgranular fracture, and ZrO2 grains were pinned at the grain boundaries, thereby enhancing the mechanical strength of the composite ceramics. Moreover, the AZS12 sample, with 12 wt.% ZrO2 and sintered at 1560°C, had the greatest flexural strength and fracture toughness of 91.6 MPa and 2.47 MPa m–1/2, respectively. Adding ZrO2 to the composite ceramics increased their flexural strength by ~37.6%.