The ordered macroporous titania were synthesized using PMMA sphere colloid crystal as template and the Sol-Gel method. The PMMA spheres were removed by calcinations. The results showed that the sol of Ti(BuO)₄, water, ethanol and hydrochloric acid was prepared according to volume ratio of V[Ti(BuO)₄]∶V(H₂O)∶V(EtOH)∶V(HCl) is 5∶2∶3∶1 and the gelled time was 20 h in air. Set the temperature program of calcinating PMMA spheres as follows: the rate of warming temperature was 1 ℃/min from room temperature to 250 ℃ and 2 ℃/min from 250 ℃ to 450 ℃, maintained it at 250 ℃ for 3 h, and at 450 ℃ for 8 h, the rate of decelerating temperature was 10 ℃/min from 450 ℃ to room temperature.

Key words: poly(methyl methacrylate) microsphere, titania, sol-gel method, macroporous