A new class of luminescent cyclometalated alkynylgold(III) complexes, [Au(RC∧N(R′)∧CR)(C≡ CR″)], i.e., [Au(C∧N∧C) (C≡CR″)] (HC∧N∧CH = 2,6-diphenylpyridine) R″ = C ₆H₅ 1, C₆H₄-Cl-p 2, C ₆H₄-NO₂-p 3, C₆H₄- OCH₃-p 4, C₆H₄-NH₂-p 5, C ₆H₄-C₆H₁₃-p 6, C₆H ₁₃ 7, [Au(^tBuC∧N∧C^tBu)(C≡CC ₆H₅)] 8 (H^tBuC∧N∧C^tBuH = 2,6-bis(4-tert-butylphenyl)pyridine), and [Au(C∧NTol∧C)(C≡CC ₆H₄-C₆H₁₃-p)] 9 (HC∧NTol∧ = 2,6-diphenyl-4-p-tolylpyridine), have been synthesized and characterized. The X-ray crystal structures of most of the complexes have also been determined. Electrochemical studies show that, in general, the first oxidation wave is an alkynyl ligand-centered oxidation, while the first reduction couple is ascribed to a ligand-centered reduction of the cyclometalated ligand with the exception of 3 in which the first reduction couple is assigned as an alkynyl ligand-centered reduction. Their electronic absorption and luminescence behaviors have also been investigated. In dichloromethane solution at room temperature, the low-energy absorption bands are assigned as the π-π* intraligand (IL) transition of the cyclometalated RC∧N(R′)∧CR ligand with some mixing of a [π(C≡CR″) → π*(RC∧N(R′)∧CR)] ligand-to-ligand charge transfer (LLCT) character. The low-energy emission bands of all the complexes, with the exception of 5, are ascribed to origins mainly derived from the π-π* IL transition of the cyclometalated RC∧N(R′)∧CR ligand. In the case of 5 that contains an electron-rich amino substituent on the alkynyl ligand, the low-energy emission band was found to show an obvious shift to the red. A change in the origin of emission is evident, and the emission of 5 is tentatively ascribed to a [π(C≡CC₆H₄NH ₂) → π*(C∧N∧C)] LLCT excited-state origin. DFT and TDDFT computational studies have been performed to verify and elucidate the results of the electrochemical and photophysical studies.