One pot facile synthesis of ordered mesoporous alumina-supported zirconia with high thermal stability and large pore sizes by evaporation-induced method was systematically investigated. The strategy based on a sol-gel process associated with nonionic triblock copolymers PPO-PEO-PPO as templates in ethanolic solution. Small-angle XRD, TEM, and nitrogen adsorption and desorption results showed that these composites possessed an ordered 2D hexagonal mesostructure, resisted to high temperature up to 1000 °C, and had large surface areas and narrow pore-size distributions. Loaded with palladium, the mesoporous alumina-zirconia composite exhibited high catalytic activity in Suzuki coupling of 2-bromotoluene with phenylboronic acid.