Ceramic hollow spheres were produced by a sacrificial template technique with subsequent sintering under temperatures ranging from 1100 °C to 1250 °C. The effect of the sintering temperature on the structure of the ceramic hollow spheres was investigated by optical and scanning electron microscopy, and a gas adsorption method. The results show that the structure of the ceramic hollow spheres can be controlled, with the retention of the hollow spherical shape, by variation of the sintering temperature. Increase of the sintering temperature from 1100 °C to 1250 °C decreased the outer diameter of the ceramic hollow spheres by 14 percent, the shell thickness by 18 percent, and the void area ratio of the shell surface by 9.2 times; both of the specific surface area and the total pore volume of ceramic hollow spheres decreased by 60 percent.