The effect of SiO2 addition on the anatase-to-rutile phase transition was investigated by DTA, XRD, FTIR, and XPS. TiO2 xerogels containing SiO2 up to 20 mol% were prepared by mixing and hydrolyzing titanium tetraisopropoxide (TTIP) and tetraethylorthosilicate (TEOS) with HNO3 as a catalyst. With increased amounts of SiO2 in the xerogels, the following results mere obtained: (1) the crystallization temperature of anatase increased from 415 degreesC in pure TiO2 to 609 degreesC in 20-mol%-SiO2-containing xerogel in the DTA curves; (2) the formation temperature of rutile, according to quantitative XRD analysis, increased with increased SiO2 content up to 5 mol% SiO2 but became constant at higher SiO2 contents; (3) the crystallinity of anatase became lower; and (4) the lattice parameter a of the anatase decreased slightly, but the parameter c decreased greatly up to 20 mol% SiO2, Although the added silicon atoms were considered from these results to be incorporated into the amorphous TiO2 and anatase structures, the Si-29 MAS NMR spectra of the xerogels containing 10 mol% SiO2 showed only tetrahedral silicon, with no indication of silicon in octahedral coordination, When calcined at higher temperatures, the xerogel showed polymerization of the SiO4 tetrahedra in the NMR spectra and the Si-O-Si vibration in the FTIR spectra, The chemical composition of the xerogel surfaces, measured using XPS, showed increased SiO2 content with increased calcining temperature, indicating the expulsion of silicon from inside the particles to form an amorphous SiO2 surface layer, The formation of this amorphous SiO2 surface layer was considered to be important in retarding the anatase-to-rutile phase transition by suppressing diffusion between anatase particles in direct contact and limiting their ability to act as surface nucleation sites for rutile. These effects of silicon additions were similar to those observed in the gamma -Al2O3-to-alpha -Al2O3 transition.