A new pentacyclic building block, benzodibenzofuranquinone (BDBFQ), is synthesized in a single step from the inexpensive and readily available feedstocks chloranil and 3bromophenol. This versatile repeat unit is incorporated into a series of conjugated materials as either the redox active quinone form or as an electron-rich dialkylated benzodibenzofuran (BDBF) unit. To illustrate the performance that can be obtained from these systems, optical and electrochemical properties were studied via UV-vis-NIR spectroscopy and cyclic voltammetry. Thin-film morphology was characterized via grazing incidence wide-angle X-ray scattering with thin-film fieldeffect transistor measurements further demonstrating the utility of this system. (C) 2017 Wiley Periodicals, Inc.