The synthesis, excited-state dynamics, and applications of two series of air-stable luminescent tungsten(VI) complexes are described. These tungsten(VI) complexes show phosphorescence in the solid state and in solutions with emission quantum yields up to 22% in thin film (5% in mCP) at room temperature. Complex 2c, containing a 5,7-diphenyl-8-hydroxyquinolinate ligand, displays prompt fluorescence (blue-green) and phosphorescence (red) of comparable intensity, which could be used for ratiometric luminescent sensing. Solution-processed organic light-emitting diodes (OLEDs) based on 1d showed a stable yellow emission with an external quantum efficiency (EQE) and luminance up to 4.79% and 1400 cdm(-2) respectively. These tungsten(VI) complexes were also applied in light-induced aerobic oxidation reactions.