Liquid-crystalline (LC) behavior and photoluminescent properties of a gold(I) complex, 2 were investigated. It was confirmed that the complex showed enantiotropic LC phases. In addition, we found that the complex showed strong photoluminescence in the condensed phases, but no luminescence was observed in a dilute solution. The single-crystal X-ray structure analysis suggested that the complex formed dimer in the condensed phases and the dimer formation plays crucial role in both LC behavior and photoluminescent properties.