The titanium species existing in titanium silicalite TS-1, which is prepared by hydrothermal method, were investigated using chemical analysis, XRD, FT-IR, 29Si MAS NMR, UV-VIS, ESR. It has been observed that several kinds of titanium species may exist in titanium silicalite. The form that titanium atoms incorporate into the framework of titanium silicalite synthesized using etrapropylammonium bromide (TPABr) as template differs from that using the classical method. But, the symmetry of titanium silicalite changes from monoclinic to orthorhombic with the increase of titanium content in both methods. The Ti-O2-originated from framework titanium and H2O2 has the moderate stability and may be active site in oxidation reaction. TS-1 synthesized using TPABr as template does not contain anatase, but contains a kind of partly condensed titanium species with six-fold coordination. The titanium species may correspond to 270-280 nm band in UV-VIS spectra and also can form Ti-O2-. But, this kind of Ti-O2-is very stable and cannot be catalytic active site. So, the six-fold coordination titanium species may be inactive in both the oxidation reaction and the decomposition of H2O2. The hypothesis has been further proved by the phenomena that the titanium species is easily washed off using acid, and acid treating will not influence the catalytic performance of TS-1.