<p>A magnetically retrievable Ni-doped CuFe₂O₄-supported MIL-101(Fe) (NCF@FM) photocatalyst was fabricated using a hydrothermal approach and utilized for the photocarboxylation of haloarenes using CO₂. This work highlights a pioneering study on the use of an MOF-based photocatalyst for the photocarboxylation of haloarenes with CO₂. The ferrite/MIL-101(Fe) heterojunction exhibits enhanced photocatalytic performance through efficient charge separation, broad light absorption, and synergistic redox activity from both components. The NCF@FM photocatalyst successfully converted chlorobenzene to benzoic acid within 24&#xa0;h of visible-light irradiation at room temperature, with 74% efficiency. The reaction proceeded through a single-electron transfer (SET) radical intermediate mechanism, where CO₂, acting as the C1 carbon source, abstracts a photogenerated electron generated upon excitation of the catalyst to produce CO₂^•− radical, which then transfers the lone electron to the halobenzene via SET to generate an aryl radical anion (C₆H₅X^•−). The highly unstable radical anion rapidly eliminates a halide ion (X⁻), generating an aryl radical (C₆H₅^•) as an intermediate species. This C₆H₅^• radical readily couples with the CO₂^•− radicals to form the final carbonylated product (C₆H₅COO⁻). Overall, this study presents a promising approach to photocarboxylation reactions using CO₂ under visible-light irradiation. This further underscores the broader potential of MOF-based systems for CO₂ utilization and organic transformation reactions.</p> Graphical Abstract <p></p>