A series of triangular, shape-persistent arylene–ethynylene macrocycles (AEMs) of related structures were synthesized and studied, with a focus on their mesomorphic behavior in correlation with their chemical structure. Generally, these discotic molecules decorated with flexible side chains demonstrated a propensity to form thermotropic liquid-crystalline (LC) phases. Characterized by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction (XRD), four of the eight investigated macrocycles manifested thermodynamically stable mesophases, featuring discotic nematic or columnar structures. Longer alkyl side chains were found more conducive to mesophases, and the alkoxycarbonyl functionality was a more effective side-chain linkage at inducing and stabilizing the LC states than the alkoxy side group. The size and structure of the cyclic aromatic backbone influenced both the occurrence and type of mesophase exhibited.