Hexacene and larger fused rings remain elusive targets for chemists. Here, we report a hexacene-like molecule containing six linearly fused rings, specifically a pentacene molecule fused with a terminal thiophene ring, pentaceno[2,3-b]thiophene. It can be purified and isolated as a purple-black powder at ambient conditions. This molecule has a low HOMO-LUMO gap of 1.75 eV in o-DCB and an optical band gap of 1.58 eV in thin film. Top contact organic thin film transistors (OTFTs) were made, and atomic force microscopy (AFM) reveals a dendritic thin film growth characteristic of pentacene. An OTFT mobility of 0.574 cm ²/V s was measured for pentaceno[2,3-b]thiophene under nitrogen.