An effective Ag/TS-1 (0.06 wt %) catalyst for oxidative desulfurization of organic sulfur in gasoline was prepared by equal-volume impregnation. The Ag species is highly dispersed, and obvious particles of the Ag species cannot be observed directly in the TEM image. The EDX mapping of a chosen line 1 in the STEM image of the catalyst by line scanning confirmed the existence of the Ag species. It was not homogeneously or randomly dispersed in any part of the titanium silicalite. In fact, they prefer to deposit around Ti species of TS-1 catalyst. A large amount of Ag loading will adversely influence the performance of TS-1 because it will sterically hinder the oxidation of organic sulfur. The oxidative desulfurization of FCC gasoline was carried out over the Ag/TS-1 catalyst with H2O2 as the oxidant and water as the solvent. The results showed that the sulfur content in FCC gasoline was lowered from 136.5 to 18.8 mu g/g after 4 h.