The interaction of H2O2 with TS-1 has been investigated by the ESR technique. A well manufactured TS-1 has been considered, where the presence of extra-structural titanium can be excluded. The two main signals observed are attributed to oxygen radical species co-ordinated on structural titanium sites, and the relevant effect of water presence in the paramagnetic complex is discussed. A comparison is performed with O2-/Ti species in TS-1 obtained by reduction/re-oxidation procedures of Ti(IV). Moreover, some possible structural configurations of the paramagnetic sites are proposed, for two of which ab initio calculation yield g(z)-values quite close to the experimental ones.