The polystyrene(PS) microspheres were prepared from free radical polymerization of styrene by a sol-gel method combined with centrifugal sedimentation. And the ordered macroporous titania was prepared from Ti(BuO)4 in ethanol solution using the mentioned PS microspheres as a template, which was removed from titania by calcination at 450 ℃. SEM images revealed the PS template has a three-dimentional ordered structure with particle diameter of ca. 450 nm and the macroporous titania thus obtained has a pore size of ca. 300 nm. XRD showed the macroporous titania has anatase structure.