With a view to combining the desirable electronic and photochemical properties of hexabenzocoronene (HBC) and the C–C bond forming capabilities of thiophenes, 1-(3-thienyl)-2,3,4,5,6-penta(4-tert-butyl-phenyl)benzene (1) was oxidised using FeCl₃. The resulting products, superaromatic thiophene (2) and its 5,5′-dimer (3), are S-HBC systems and provide a new pair of spectral comparators.