The solvothermal reaction of titanium isopropoxide and chromate in the presence of benzoate produced two novel host-guest clusters encapsulating Cs+ or H3O+, (H3O)@Ti7Cr14 and Cs@Ti7Cr14. The most remarkable feature is that the Ti7O7 ring is concentrically embraced by a Cr14O14 ring to form a rigid Ti7Cr14 host. ESI-MS and 133Cs NMR revealed that the overall framework structures are preserved, whereas the benzoate ligands on the two clusters may be labile in solutions. Both (H3O)@Ti7Cr14 and Cs@Ti7Cr14 exhibit good UV-vis light-responsive properties and photocatalytic activities, with absorption edges extending up to 780 nm. Cs@Ti7Cr14 is an effective visible-light-responsive photocatalyst in both the heterogeneous methylene dye degradation and homogeneous CO2 cycloaddition reaction under mild conditions like room temperature and 1 bar of CO2. According to the mechanism studies, Cs+, as a rigid guest, can significantly improve the photogenerated charge separation efficiency of the Ti7Cr14 host, thereby improving its interface charge separation properties, photocurrent, and photocatalytic activities. Our findings not only provide new members of heterometallic titanium oxide clusters to enrich the metal oxide cluster family but also open up new possibilities for their photoresponses, which may play an important role in solar energy harvesting for sustainable chemistry.