<p>In this study, TiO<sub>2</sub> powder was used as the additive to directly blend with raw bituminous coal and coking coal for preparing modified activated carbon (Ti/AC) by one-step carbonization-activation method. The Ti/AC samples were prepared through blending with different ratios of TiO<sub>2</sub> (0–12 wt%) and their desulphurization performance was evaluated. The results show that the desulphurization activity of all Ti/AC samples was higher than that of the blank one, and the highest breakthrough sulphur capacity was obtained at 200.55 mg/g C when the blending ratio of TiO<sub>2</sub> was 6 wt%. The Brunauer-Emmett-Temer results show that the micropores were dominant in the Ti/AC samples, and their textual properties did not change evidently compared with the blank one. The X-ray photoelectron spectroscopy results show that the loaded TiO<sub>2</sub> could influence the relative content of surface functional groups, with slightly higher content of π–π* transitions groups on the Ti/AC samples, and the relative contents of C=O and π–π* transitions groups decreased evidently after the desulphurization process. The X-ray diffraction results show that the anatase TiO<sub>2</sub> and rutile TiO<sub>2</sub> co-existed on the surface of the Ti/AC samples. After the desulphurization process, TiO<sub>2</sub> phases did not change and Ti(SO<sub>4</sub>)<sub>2</sub> was not observed on the Ti/AC samples, while sulphate was the main desulphurization product. It can be assumed that SO<sub>2</sub> could be catalytically oxidized into SO<sub>3</sub> by TiO<sub>2</sub> indirectly, rather than TiO<sub>2</sub> directly reacted with SO<sub>2</sub> to Ti(SO<sub>4</sub>)<sub>2</sub>.</p