Liquid crystals (LCs) of large macrocyclic compounds are a plausible platform in which to organize included guest molecules regularly in a flowable medium. Herein, a series of metallomacrocycles with different peripheral alkyl chains were synthesized through a 3:3 self-assembly based on metal complexation between naphthalene-2,7-dihydroxamic acid and Cu2+ ions. The crystallinity and liquid crystallinity of the macrocycles sharply depend on the structure of the peripheral alkyl chains. The metallomacrocycle with six hexyl chains has only the crystalline phase, whereas the metallomacrocycles with more and longer side chains exhibit LC mesophases. Most notably, oligo(ethylene glycol) side chains effectively assemble the macrocycle into an ordered lamellar structure.