Star-shaped triphthalocyaninehexaazatriphenylene 1 was synthesized via condensation between a new building block 1,2-diaminophthalocyanine and cyclohexanehexaone. Compound 1 represents the largest star-shaped phthalocyanine-fused hexaazatriphenylene reported so far. This largely expanded phthalocyanine shows good solubility and has a strong tendency to aggregate both in solution and on the surface, indicating its potential as an active component in organic electronic devices.