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This study aims to examine the mechanical, shrinkage and chemical properties of photocatalytic cementitious materials containing synthetic fibers and a shrinkage-reducing admixture (SRA). Two types of titanium dioxide (TiO₂) powders and white Portland cement were considered along with ordinary Portland cement (OPC) as a control. Two types of synthetic fibers, i.e., glass and polyethylene (PE), and an SRA with contents varying from 0% to 3% were also considered. Using the TiO₂ powders and the white Portland cement was effective in reducing the nitrogen oxides (NO<i>_x</i>₎ concentration in cement composites. The use of PE fibers was more effective than glass fibers in terms of the mechanical properties, i.e., the compressive strength and tensile performance. With the addition of TiO₂ powders and SRA or the replacement of OPC with white cement, the mechanical properties of the cement mortar generally deteriorated. The total shrinkage of the mortar could be reduced by incorporating the fibers at volume fractions greater than 1%, and the glass fiber was more effective than the PE fiber in this regard. The TiO₂ powders had no significant impact on the shrinkage reduction of the cement mortar, whereas the SRA and the white Portland cement effectively reduced shrinkage. The addition of 3% SRA decreased the total shrinkage by 43%, while the replacement of the OPC with white cement resulted in a 20% reduction in the shrinkage.