Zr-containing SBA-15 materials with hollow spherical morphology were synthesized via adding zirconium into SBA-15 synthesis solution and adjusting pH to about 4-5 with ammonia water. The hollow spherical mesoporous materials were observed in micron scale, and the shell thickness was about 100 nanometers. Zirconium was well dispersed inside the mesoporous structure. The sulfated hollow Zr-doped SBA-15 spheres showed better catalytic activity than conventional SBA-15 spheres in dehydration reactions.