The X-ray crystal structure and photophysical properties of 1,6,7,12,13,18,19,24-octamethylacenaphthyleno[b,l]tetraphenylene, which has been synthesized via a Diels-Alder reaction of 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctene and 6,7-dihydro-6-hydroxy-7,9-dimethyl-8H-cyclopenta[a]acenaphthylene-8-one, are reported.