Abstract: Titanium silicalite (TS-1) zeolites with different distribution of Ti species were synthesized through altering different amounts of (NH₄)₂SO₄ as crystallization-mediating agent. The distribution of titanium species of TS-1-X samples (X represents the molar ratio of (NH₄)₂SO₄ to SiO₂) was systematically investigated via ICP-AES, FT-IR, UV-Vis, UV-Raman and other techniques. The TS-1-X zeolite samples were applied in the epoxidation of 1-hexene reaction. It was found that the appropriate amount of ammonium salt not only facilitated the enrichment of titanium species from liquid phase to solid phase and promoted the incorporation of Ti into the MFI skeleton, but also resulted in the formation of uniformly small TS-1 crystals due to the inhibition of rapid growth of crystals. However, much more amounts of (NH₄)₂SO₄ led to the formation of extra-framework Ti, including anatase TiO₂ and amorphous Ti species. Meanwhile it promoted the rapid growth of grain resulting in larger TS-1 crystals. Ti-rich TS-1 sample synthesized with molar ratio of (NH₄)₂SO₄ to SiO₂ of 0.2 exhibited higher conversion of 1-hexene (42 %) and effective utilization of H₂O₂ (81.8 %). In addition, the effect of ammonium salt’s composition on the properties of TS-1 was investigated by experiments and characterizations. It was found that ammonium salt could regulate the process of crystallization through its own anion and changing PH of the synthesis gel.