An unusual oligomerization/oxidation reaction of a 3‐boron‐substituted 1‐phenylbuta‐1,3‐diene produces 6,9,16,19‐tetraphenyl‐5,15‐distyryl‐3,13,25,26‐tetraoxa‐2,12‐diborapentacyclo[16.2.2.28,11.12,5.112,15]hexacosa‐1(20),7,10,17‐tetraene

The unusual title macrocyclic structure, C60H54B2O4, has been isolated from exposure of 3-BF3-1-phenyl­buta-1,3-diene to both air and moisture in an attempt to obtain crystals of the starting butadiene compound. Formation of the macrocycle from six mol­ecules of the starting butadiene material is rationalized and its structural features are compared with those of other B(OR)2-substituted cyclo­hexane and benzene ring containing structures. Mol­ecules reside on crystallographic centers of inversion and there are no inter­molecular inter­actions of note in the crystal structure.