em, we demonstrate that excitons can be effectively dissociated into charge carriers with the incorporation of oxygen vacancy, leading to excellent performances in charge-carrier-involved photocatalytic reactions such as superoxide generation and selective organic syntheses under visible-light illumination. This work not only establishes an in-depth understanding of defective structures in photocatalysts but also paves the way for excitonic regulation via defect engineering.1f:T4f3,Selective organic transformation under mild conditions constitutes a challenge in green chemistry, especially for alcohol oxidation, which typically requires environmentally unfriendly oxidants. Here, we report a new plasmonic catalyst of Au supported on BiOCl containing oxygen vacancies. It photocatalyzes selective benzyl alcohol oxidation with O₂ under visible light through synergistic action of plasmonic hot electrons and holes. Oxygen vacancies on BiOCl facilitate the trapping and transfer of plasmonic hot electrons to adsorbed O₂, producing •O₂^- radicals, while plasmonic hot holes remaining on the Au surface mildly oxidize benzyl alcohol to corresponding carbon-centered radicals. The hypothesized concerted ring addition between these two radical species on the BiOCl surface highly favors the production of benzaldehyde along with an unexpected oxygen atom transfer from O₂ to the product. The results and understanding acquired in this study, based on the full utilization of hot charge carriers in a plasmonic metal deposited on a rationally designed support, will contribute to the development of more active and/or selective plasmonic catalysts for a wide variety of organic transformations.20:T4f2,Abstract Most organic compounds are conventionally synthesized under high temperature and elevated pressure, resulting in significant energy consumption and wastage. Heterogeneous photocatalytic oxidation has the potential to provide a green route for the synthesis of the majority of industrially important chemicals. The major limiting factor affecting the efficiency of photocatalytic organic synthesis is the lack of high selectivity; therefore, substantial effort has been devoted to solving this problem. Responding to this fast‐moving progress, this review gives an overview of the fundamental understanding of the reactive oxygen species involved in photocatalytic organic oxidations and furthermore, the general mechanisms of a few crucial oxidation reactions. The focus of this critical review is on the discussion of diverse strategies to improve the selectivity of high value chemicals, including band engineering, metal loading, hybrid materials, and defect engineering, with the primary aim of highlighting the catalyst design protocols based on the reaction mechanism. Finally, the difficulties and challenges of developing highly selective oxidation photocatalysts are comprehensively discussed in order to help direct the focus of future research.21:T493,Sluggish charge kinetics and low CO₂ affinity seriously inhibit CO₂ photoreduction. Herein, the synchronous promotion of charge separation and CO₂ affinity of Bi₄ Ti₃ O₁₂ is realized by coupling corona poling and surface I-grafting. Corona poling enhances ferroelectric polarization of Bi₄ Ti₃ O₁₂ by aligning the domains direction, which profoundly promotes charge transfer along opposite directions across bulk. Surface I-grafting forms a surface local electric field for further separating charge carriers and provides abundant active sites to enhance CO₂ adsorption. The two modifications cooperatively further increase the ferroelectric polarization of Bi₄ Ti₃ O₁₂ , which maximize the separation efficiency of photogenerated charges, resulting in an enhanced CO production rate of 15.1 μmol g^-1 h^-1 (nearly 9 times) with no sacrificial agents or cocatalysts. This work discloses that ferr

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