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The syntheses and mesomorphism of novel octaalkoxymethyl-substituted tetra-2,3-thiophenophorphyrazines, heterocyclic phthalocyanine analogues in which the benzene rings are replaced by thiophene rings, are reported. NMR analysis indicates that these materials exist as isomeric mixtures due to the asymmetry induced by the thiophene ring. Among the attractive features of liquid-crystalline 2,3-thiophenophorphyrazines over phthalocyanines are their lower mesomorphic and isotropic temperatures. These features have resulted in liquid crystallinity at room temperature. Similar to liquid-crystalline phthalocyanine derivatives, metalation with copper raises the transition temperatures.