Co(III)-catalyzed highly regio- and stereoselective direct C6 olefination of 2-pyridones with alkynes has been developed with the assistance of chelation. Upon variation of the reaction conditions, 2-pyridones react well with diaryl alkynes via a C6 olefination/directing group migration pathway to give the tetrasubstituted 6-vinyl-2-pyridones, but the C6-H olefination with terminal alkynes works effectively to afford only the C6-olefinated 2-pyridones. A judicious choice of a solvent and an additive is crucial for catalysis. The protocols feature 100% atom economy, excellent site selectivity, high stereoselectivity, an ample substrate scope, and good compatibility of functional groups. Synthetic applications are demonstrated, and experimental studies and density functional theory calculations are conducted to gain mechanistic insight into the two transformations.