The complex sulfur-containing compounds has become a concern during municipal sewage sludge (MSS) coprocessing in cement kiln. In this study, mesoporous titanium dioxide catalysts loaded with phosphotungstic acid (HPW) are prepared by self-assembly synthesis method and dipping method, the HPW-TiO2 catalysts was characterized by several tests. The experimental results show that the self-assembly method results in larger specific surface area and more acidic sites. The catalysts were mixed and cotreated with MSS at preheated kiln temperatures of cement kiln (200 °C/260 °C/320 °C), and the catalytic properties and reaction mechanism was measured by X-ray photoelectron spectroscopy (XPS). The mesoporous HPW-TiO2 prepared by polymer-oriented method shows more effective oxidation catalytic properties for the complex sulfur-containing organic compounds in MSS. The catalysts promote the oxidation reaction of both aromatic-S and aliphatic-S in MSS at different temperatures with molecular oxygen as the oxidizing agent, the organic sulfide was converted to sulfoxide and further oxidized to sulfone.