A novel liquid-crystalline (LC) gold(I) complex (Biph6) having biphenyl acetylene ligand was designed and synthesized, and its LC behavior and photoluminescence properties were compared with those of a previously reported gold complex (Ph6) with phenyl acetylene ligand. Biph6 exhibited an enantiotropic nematic phase in a temperature range wider than that of Ph6. Ph6 and Biph6 showed intense photoluminescence with different colors in the crystalline phase: blue and yellowish green luminescence, respectively. We demonstrated that the color of luminescence of the gold complexes could be changed by changing the structure of the molecules and molecular aggregates.