<p>Catalytic desulfurization study in concentrated liquid waste of herbal decoctions has attracted more and more attention for meeting the stringent waste water discharge standards but remains a challenge that the catalysts are effectiveness for sulfur-containing organic compound and inorganic compound at the same time. Benzothiophene (BT) was chosen as the simulated compound for sulfur-containing organic, and Na₂S was chosen as the simulated compound for sulfur-containing inorganic. The high total sulfur removal was achieved by investigating a new kind of framework-substituted Mn-TiNTs catalyst. The desulfurization rate nearly 90% was found in complex concentrated liquid waste of herbal decoctions under the optimum condition. Additionally, the mechanism of oxidative desulfurization over Mn-doped skeleton heteroatom titanium nanotubes was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM).</p>