The Cu(II)-catalyzed and chelate-directed C6-selective C–H thiolation of 2-pyridones with disulfides was developed to provide aryl and alkyl thioethers. This transformation uses a catalytic amount of Cu(OAc)₂ and molecular oxygen in air as an oxidant, no cocatalysts or metallic oxidants are required. The reaction accommodated both electronic and steric factors at the C3–C5 positions of 2-pyridones, which is efficient for the C6 thiolation of a broad range of 2-pyridones with up to 93% yield.