Herein, we report a bromide-mediated, C2-selective, and oxygenative alkylation of pyridinium salts using alkenes and O₂ for the synthesis of important β-2-pyridyl ketones. Notably, a quaternary carbon center was successfully installed at the C2-position of pyridine and the resulting C2-substituents were highly functionalized. The intermediary cycloadduct was isolated and further transformed into the desired product, which indicated that this three-component reaction underwent a reaction cascade including dearomative cycloaddition and rearomative ring-opening oxygenation. Finally, the bromide-mediated mechanism was discussed and active Br(I) species were proposed to be generated in situ and promote the rearomative ring-opening oxygenation by halogen bond-assisted electron transfer.