Abstract Photocatalytic technology could efficiently treat U(VI) from aqueous and simulated seawater conditions, which is critical for the sustainable development of nuclear energy. Herein, TiO2@surface sulfate functionalized CdS double-shell hollow nanosphere (TiO2@[SO4]/CdS-x) was constructed and applied for photocatalysis reduction of U(VI). The introduction of [SO4]/CdS could facilitate separation and transfer of photogenerated electron-hole, and accelerate U(VI) diffusion to promote photocatalytic reactions kinetics. Accordingly, the TiO2@[SO4]/CdS-2 (the mass ratio of 16.8%) could completely remove U(VI) illuminated for 10 min in 3 mmol·L−1 of NaHCO3 and maintain 88% after five cycles, and the apparent rate constant is 59 and 16.5 times as much as TiO2 hollowspheres and [SO4]/CdS. Additionally, the electron transfer at TiO2@[SO4]/CdS-2 interface conforms to Z-type conduction mechanism that promotes the photogenerated electrons collected on [SO4]/CdS surface, cooperating with superoxide radicals to reduce U(VI) to α-U3O8. These results indicate the great application of double-shell hollow nanospheres photocatalysts for uranium recovery from seawater.