Abstract Mesoporous hollow spheres have attracted attention because of their high specific surface areas, well-ordered mesopores, and unique void spaces. However, development of effective approaches for synthesis of the mesoporous hollow spheres with an ordered mesopores remains difficult challenge. Herein, we report an approach to synthesize mesoporous silica–zirconia composite hollow spheres via a sol-gel reaction using polystyrene template particles. We found that controlling cetyltrimethylammonium bromide concentration led to a formation of uniform mesopore in silica–zirconia composite shells. In addition, we investigated the effect of the mesoporous hollow spheres in the present study on the hydrolysis of ammonia borane. The hydrolysis reaction was completely finished in the presence of the mesoporous hollow spheres. The mesoporous hollow spheres exhibited a substantially higher amount and rate of hydrogen evolution than the hollow spheres reported in previous studies because of their larger amount of acid sites.