<jats:p>Isocoumarins are an important class of bicyclic lactones, which are seen in natural products, drugs, and bioactive compounds, and a variety of synthetic methods of isocoumarins have been developed. However, the synthesis of isocoumarins via the catalytic CO2 fixation has been scarcely reported despite the potential incorporation of CO2 into the lactone moiety. Here, we developed the light‐driven carboxylative cyclization reaction of o‐ethynyl aryl bromides with CO2, which selectively produced isocoumarins. Control experiments revealed that photoirradiation promoted the cyclization process with high selectivity.</jats:p>
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