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This study focuses on the relationship between photo-catalytic performance and optical property over Si-incorporated TiO2. The Siincorporated TiO2 particles exhibited a pure structure of anatase having a particle size of less than 20 nm and surface area of more than 190 m2/g. The absorbance did not shift to a higher wavelength in spite of the incorporation of the Si ions, but the intensity of the photoluminescence (PL) curve was the smallest in the case of the 2.0 mol% Si-TiO2, which was related to the recombination between the excited electrons and holes. Based on these results, the photodecomposition of methyl orange in the liquid reaction was enhanced over the 2.0 mol% Si-incorporated TiO2 compared with that over pure TiO2: Methyl orange at 10.0 ppm was completely decomposed after 100 min when 1.0 g of the 2.0 mol% Siincorporated TiO2 was used.