Dithienoacenes with a heptacene core, heptaceno[2,3-b:11,12-b ‘]bis[1]benzothiophene, have been synthesized through the combination of solution and surface assisted chemistry. The atomic composition, structural arrangement and electronic properties of the molecules on the Au(111) surface have been deeply explored by non-contact atomic force microscopy (nc-AFM), bond-resolved scanning tunnelling microscopy (BR-STM) and scanning tunneling spectroscopy (STS) corroborated by density functional theory (DFT) calculations. Our combined experiments reveal modifications induced by sulfur substitution. Dithienoacenes with a heptacene core, heptaceno[2,3-b:11,12-b ‘]bis[1]benzothiophene, have been synthesized through the combination of solution and surface assisted chemistry.