The paper reports a novel, kinetically controlled method for the direct carboxylation of unactivated secondary alkyl bromides using a combination of photoredox and nickel catalysis. This approach overcomes the challenge of chain-walking and β-hydride elimination, which are common issues in carboxylation reactions involving secondary alkyl halides. The site-selectivity is achieved through the rapid formation of Ni(I)–alkyl species, which facilitates the insertion of CO₂ at the initial C(sp³)–Br site. Preliminary mechanistic studies reveal the importance of stereoelectronic effects in guiding the reactivity and site-selectivity. The method operates under mild conditions and exhibits excellent chemo- and site-selectivity, making it a promising tool for the synthesis of carboxylic acids from secondary alkyl halides. The authors also explore the generality of their method, demonstrating its applicability to a wide range of substrates, including challenging classes such as esters, amides, and heterocycles. The study includes detailed experimental conditions, reaction optimization, and theoretical calculations to support the proposed mechanism.The paper reports a novel, kinetically controlled method for the direct carboxylation of unactivated secondary alkyl bromides using a combination of photoredox and nickel catalysis. This approach overcomes the challenge of chain-walking and β-hydride elimination, which are common issues in carboxylation reactions involving secondary alkyl halides. The site-selectivity is achieved through the rapid formation of Ni(I)–alkyl species, which facilitates the insertion of CO₂ at the initial C(sp³)–Br site. Preliminary mechanistic studies reveal the importance of stereoelectronic effects in guiding the reactivity and site-selectivity. The method operates under mild conditions and exhibits excellent chemo- and site-selectivity, making it a promising tool for the synthesis of carboxylic acids from secondary alkyl halides. The authors also explore the generality of their method, demonstrating its applicability to a wide range of substrates, including challenging classes such as esters, amides, and heterocycles. The study includes detailed experimental conditions, reaction optimization, and theoretical calculations to support the proposed mechanism.