The photoreduction of uranium over TiO₂ provides an important pathway to uranium resource utilization and pollution abatement. However, the impact of the TiO₂ crystalline type on photocatalytic reduction of U(VI) is still unclear. In this study, the influence of crystal type of TiO₂ on U(VI) photoreduction was studied. The results showed that rutile was more reactive for the photocatalytic reduction of U(VI) than anatase. Interestingly, an obvious synergistic effect was observed for mechanically mixed rutile-anatase and the photoconverted UO₂ particles preferred to precipitate on rutile surface. The optimum efficiency was achieved for the mixture containing 30 wt% anatase and 70 wt% rutile. The anatase {101} planes tended to match up with rutile {110} facets after the two minerals were mixed. The formation of rutile-anatase aggregates led to the transfer of photogenerated electrons from anatase to rutile. This process could prolong the lifetime of carriers, facilitating U(VI) reduction.