The TiO2/multiwalled carbon nanotube (MWCNT) composites were prepared by hydrothermal deposition. Batch experiments were carried out to study the removal of Cr(VI) from aqueous solution to TiO2, MWCNTs and TiO2/MWCNTs. Scanning electron microscopy and X-ray diffraction were utilized to characterize the prepared TiO2/MWCNT composites. The introduction of MWCNTs onto TiO2 catalyst led to a remarkable increase of Cr(VI) removal through adsorption and photocatalytic reduction under ultraviolet irradiation. Results of X-ray photoelectron spectroscopy analysis of chromium species adsorbed on TiO2/MWCNTs phase revealed that the removal mechanism of Cr(VI) by TiO2/MWCNTs under UV-irradiation was the reduction of Cr(VI) into Cr(III). The adsorption and photocatalytic activity of Cr(VI) decreased with increasing in pH, and was not affected by the concentration of sulphate obviously. In the ternary systems humic acid (HA)/fulvic acid (FA)-Cr(VI)-TiO2/MWCNTs, the increasing of FA/HA concentration did not cause any drastic changes in the adsorption capacity in terms of Cr(VI) concentration in the dark, but a minor increasing trend for the photocatalytic reduction of Cr(VI). The presence of humic substances enhanced the photocatalytic reduction and adsorption of Cr(III) to TiO2/MWCNTs.