Luminescent liquid-crystalline (LC) Au complexes with various aromatic cores and flexible terminal chains were synthesized. The aromatic core aspect ratio crucially affected the LC temperature range and melting point of the complexes. Moreover, branched flexible chains reduced the melting point, thus expanding the LC temperature range. In the crystalline and LC phases of the complexes, fluorescence was quenched by the aggregation-caused quenching effect, but phosphorescence was enhanced by the crystallization-induced phosphorescence effect. However, no phosphorescence was observed in the isotropic phase. Thus, not only aggregation but also regularity of molecular aggregates is necessary for the observed crystallization-induced phosphorescence effect.