AbstractBackgroundThere has been a continuous interest in the development of luminescent gold(III) complexes as emitters for OLED applications in recent years.ObjectiveTo design and synthesize a series of luminescent bis‐alkynylgold(III) complexes with bidentate C^N‐type ligands and to compare their properties with related tridentate cyclometalated complexes.MethodsA series of bis‐alkynylgold(III) complexes with bidentate C^N‐type ligands derived from 2‐phenylpyridine and 7,8‐benzoquinoline has been designed and synthesized. The photophysical properties of the complexes have been studied by electronic absorption and emission spectroscopies.ResultsAll of the complexes were observed to exhibit rich photophysical and electrochemical properties. In particular, the complexes were strongly emissive at ambient conditions, showing vibronic‐structured emission bands peaked at 433–557 nm in dichloromethane solutions at 298 K.ConclusionsBy comparing the structural features, luminescence properties and electrochemistry of the bidentate complexes with related tridentate C^N^C and C^N^N‐type alkynylgold(III) complexes, a better understanding on the structure‐property relationship of the alkynylgold(III) system has been obtained.