2,3,5,6,8,9-hexabromosumanene (2) with Br groups at all the peripheral aromatic carbons was successfully synthesized. Single-crystal X-ray structural analysis of 2 revealed the formation of a one-dimensional columnar structure in the solid state, where the molecules overlapped in an eclipsed manner. The Suzuki-Miyaura cross-coupling of 2 and various aryl-boronic acids gave hexaarylsumanene derivatives (3a-3h) in good-to-moderate yields. The NMR spectroscopic analysis and theoretical calculations of 2 and hexaphenylsumanene (3a) revealed that the six peripheral functional groups do not significantly affect the original bowl structure or bowl-to-bowl inversion behavior of sumanene.