Incorporation of 7,7,8,8-tetracyanoquinodimethane (TCNQ) moieties into the acene backbone has been successfully achieved and two heptacene-TCNQ derivatives and one nonacene-TCNQ derivative have been synthesized and well characterized. Two TCNQ moieties have been embedded into heptacene and nonacene backbones for the first time. All the three compounds have good stability and solubility due to the presence of TCNQ moieties. Single crystal analysis revealed a bent butterfly-like conformation of these molecules. Their charge transport properties have been characterized using organic field effect transistors (OFETs). © 2013 The Royal Society of Chemistry.