Herein we report the syntheses, X-ray structures and photophysical studies of the dinuclear dimeric gold(i) complexes [ClAu(C6H5N)(PPh2)2]2 (1), [Au(C6H5N)(PPh2)2]2[SbF6]2 (2) and [Au(2,6-Me2C6H3N)(PPh2)2]2[SbF6]2 (4). We have used ligands with different substituents to see the effect of the substituents on the photophysical properties. All these complexes feature strong intramolecular AuAu interactions (2.7987-3.0056 Å) and were found to exhibit excellent luminescence properties with high quantum yields as well as different colors of emission.