In article number 1702928, Indrajit Shown, Li‐Chyong Chen, Kuei‐Hsien Chen, and co‐workers report a black titania with dual active sites (Ni‐nanoclusters and oxygen vacancy) for photocatalytic carbon dioxide (CO2) reduction via artificial photosynthesis with H2O and simulated sunlight. The intentionally introduced dual active sites lead to not only high photocatalytic activity, but also to selective solar fuel production under simulated solar light. The CO2 adsorption and activation capability of the catalyst is demonstrated using computational study and the underlying mechanism in charge transfer and product formation is highlighted.