We have synthesized 13,13′-(3,5-bis(trifluoromethyl)phenyl)-6, 6′-bipentacene from a soluble bispentacenequinone precursor. Bispentacene takes orthogonal conformation in the solid state and exhibits four reversible redox potentials. In addition, a tetracyanobipentacenequinodimethane was obtained for the first time from the pure bispentacenequinone. © The Royal Society of Chemistry 2013.