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Abstract Electrosynthesis of alkyl carboxylic acids upon activating stronger alkyl chlorides at low‐energy cost is desired in producing carbon‐rich feedstock. Carbon dioxide (CO₂), a greenhouse gas, has been recognized as an ideal primary carbon source for those syntheses, and such events also mitigate the atmospheric CO₂level, which is already alarming. On the other hand, the promising upcycling of polyvinyl chloride to polyacrylate is a high energy‐demanding carbon‐chloride (C−Cl) bond activation process. Molecular catalysts that can efficiently perform such transformation under ambient reaction conditions are rarely known. Herein, we reveal a nickel (Ni)‐pincer complex that catalyzes the electrochemical upgrading of polyvinyl chloride to polyacrylate in 95 % yield. The activities of such a Ni electrocatalyst bearing a redox‐active ligand were also tested to convert diverse examples of unactivated alkyl chlorides to their corresponding carboxylic acid derivatives. Furthermore, electronic structure calculations revealed that CO₂binding occurs in a resting state to yield an η²‐CO₂adduct and that the C−Cl bond activation step is the rate‐determining transition state, which has an activation energy of 19.3 kcal/mol. A combination of electroanalytical methods, control experiments, and computational studies were also carried out to propose the mechanism of the electrochemical C−Cl activation process with the subsequent carboxylation step.