TiO2-based material was reported as a promising catalyst for desulfurization at ambient conditions. In this work, the adsorption of thiophene over the TiO2 anatase (001) surface, as well as O-poor and O-rich surfaces, has been studied by using the first principles density function theory calculations. The adsorption on the perfect surface is relatively weak according to the estimated adsorption energy, while the adsorption on the O-rich surface through S-O bonds is the strongest. The adsorption on the O-rich surface also results in electron transferring and the S-C bonds in thiophene weakening. The results are in agreement with the experimental results that the pretreatment of the TiO2-based adsorbent with oxygen improved the adsorption capacity of the adsorbent.