A new class of donor–acceptor type luminescent bis(alkynyl)gold(III) N⁁C complexes has been synthesized and characterized. These gold(III) complexes not only exhibit high photoluminescence quantum yields of up to 0.81, but also interesting mechanochromic luminescence behaviors that are reversible. Upon grinding, a dramatic luminescence color change from green to red can be observed in solid samples of the gold(III) complexes, and the mechanochromic luminescence can be readily tuned via a judicious selection of substituents on the pyridine ring. In addition, solution-processable OLEDs based on this class of complexes with EQE values of up to 4.0% have been realized, representing the first demonstration of bis(alkynyl)gold(III) N⁁C complexes as emissive materials in solution-processable OLEDs.