An electron-deficient tetrathiafulvalene (TTF)-conjugated bistetracene 2 was synthesized as the counterpart of phenyl-substituted TTF-conjugated bistetracene 1, and was characterized in the molecular electronic structures based on the spectroscopic measurements. UV–vis absorption spectrum of 2 is slightly broader than that of 1 and fluorescence spectrum of 2 is red-shifted, reflecting the red-shifted absorption spectrum. The energy level of the highest occupied molecular orbital (HOMO) of 2 was directly determined by the atmospheric-photoelectron yield spectroscopy in powder to be −5.8eV, which is remarkably lower than that of 1 (−5.2eV).