We report a ligand-free, cerium-catalyzed decarboxylative fluorination of carboxylic acids via photoinduced ligand-to-metal charge transfer (LMCT) catalysis. This method utilizes readily available carboxylic acids as radical precursors, enabling the selective formation of alkyl fluorides under mild conditions. The protocol tolerates diverse carboxylic acids with a high functional group tolerance. Mechanistic studies confirm that the reaction proceeds via alkyl radical generation through light-induced LMCT of cerium-(IV) carboxylate followed by fluorine transfer. This efficient and cost-effective strategy provides a sustainable route to fluorinated molecules relevant to pharmaceuticals and agrochemicals.