To study the electronic interactions in donor-acceptor (D-A) ensembles, D and A fragments are coupled in a single molecule. Specifically, a tetrathiafulvalene (TTF)-fused dipyrido[3,2-a:2′,3′-c]phenazine (dppz) compound having inherent redox centers has been synthesized and structurally characterized. Its electronic absorption, fluorescence emission, photoinduced intramolecular charge transfer, and electrochemical behavior have been investigated. The observed electronic properties are explained on the basis of density functional theory. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.