AbstractHerein are described the synthesis, photophysical properties and applications of a series of luminescent cyclometalated Au^III complexes having an auxiliary aryl ligand. These complexes show photoluminescence with emission quantum yields of up to 0.79 in solution and 0.84 in thin films (4 wt % in PMMA) at room temperature, both of which are the highest reported values among Au^III complexes. Thermally activated delayed fluorescence (TADF) is the emission origin for some of these complexes. Solution‐processed OLEDs made with these complexes showed sky‐blue to green electroluminescence with external quantum efficiencies (EQEs) of up to 23.8 %, current efficiencies of up to 70.4 cd A⁻¹, and roll‐off of down to 1 %, highlighting the bright prospect of Au^III‐TADF emitters in OLEDs.