In this paper, we report fabrication of hollow silica–zirconia composite spheres by polystyrene (PS) template method and control of wall thickness of the hollow spheres in nanoscale. Both the hollow spheres before and after calcination were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and powder X-ray diffraction analysis (XRD). Morphology of the hollow spheres does not significantly change after calcination from the results of SEM and TEM images, while the amount of residual PS templates drastically decreases via the calcination procedure from the results of FTIR and elemental analysis. The sample after calcination mainly includes amorphous silica from the results of XRD, indicating that the hollow silica–zirconia composite spheres consist of amorphous phases and/or fine particles. Wall thicknesses of the samples after calcination are controlled by adjusting the amount of PS template suspension, and hollow silica–zirconia composite spheres with the wall thicknesses of 17.5, 15.0, 10.0, and 2.0nm are obtained using the PS template suspension of 25.0, 33.5, 100.0, and 400.0g, respectively. The activities of the hollow spheres for hydrolytic dehydrogenation of ammonia borane (NH3BH3) were compared. The evolutions of 2.0, 3.1, 5.0, and 8.0mL hydrogen from aqueous NH3BH3 solution were finished in about 4, 5, 3, and 7min in the presence of the hollow spheres with wall thicknesses of 17.5, 15.0, 10.0, and 2.0nm, respectively. The molar ratios of the hydrolytically generated hydrogen to the initial NH3BH3 in the presence of the hollow spheres with wall thicknesses of 17.5, 15.0, 10.0, and 2.0nm are 0.5, 0.8, 1.4, and 2.0, respectively. The results indicate that the activity of hollow silica–zirconia composite spheres for hydrolytic dehydrogenation of NH3BH3 improves with decrease of wall thickness of the hollow spheres. From the results of BET adsorption measurements, specific surface area of the hollow spheres increases with decrease of wall thickness of the hollow spheres. The results of activity, specific surface area, and XRD profiles suggest that the primary particles form layer-like structure in the wall of hollow silica–zirconia composite spheres and the number of the layers depends on the wall thickness.