Poly(butyl methacrylate) (PBMA) colloidal crystal templates were assembled orderly on the clean substrates of monocrystalline silicon by dip-drawing technique and titanium dioxide (TiO2) macroporous membranes were prepared by using sol-dipping template method to fill the interstices among the PBMA templates, followed by calcination to remove the templates at 550℃. Calcination of the PBMA templates was carried out according to the following procedure: the rate of rising temperature was 5℃/min from room temperature to 150℃, 2℃/min from 150℃ to 270℃, 1℃ /min from 270℃ to 430℃, 2℃/min from 430℃ to 550℃ and maintained it at 550℃ for 2h. X-ray diffraction (XRD) spectra indicated the macroporous materials were anatase structure. The polymerization mechanism of BMA with Fenton reagent as a new initiator was discussed, and the removal process of the PBMA templates and the formation of TiO2 pore size were investigated, respectively. The results showed that the new method of polymerization overcomes many problems associated with the conventional emulsion polymerization techniques such as long reaction time, necessary deoxygenation, and complicated operation.