A new class of fused heterocyclic tridentate ligand‐containing alkynylgold(III) complexes with tunable emission color has been successfully designed and synthesized. Structural modification of the σ‐donating fused heterocyclic alkynyl ligands, including substituted fluorene, carbazole, and triphenylamine, enables a large spectral shift of about 110 nm (ca. 3310 cm−1) that covers the green to red region to be realized with the same tridentate ligand‐containing alkynylgold(III) complexes in solid‐state thin films. Interestingly, the energy of the excimeric emission can be controlled by the rational design of the fused heterocyclic alkynyl ligands. Superior solution‐processable organic light‐emitting devices (OLEDs) with high external quantum efficiencies (EQEs) of 12.2, 13.5, 9.3, and 5.2 % were obtained with green, yellow, orange, and red emission. These high EQE values are comparable to those of the vacuum‐deposited OLEDs based on structurally related alkynylgold(III) complexes.