Two novel conjugated imino-π-extended tetrathiafulvalenes with p-iminobenzene, N,N′-bis(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)benzene-1,4-diamine (1) and N,N′-bis(4,5-bis(ethylenedithio)-1,3-dithiolo-2-ylidene)benzene-1,4-diamine (2), have been synthesized and characterized by NMR, IR, MS and X-ray single-crystal diffraction. Both the two targets adopt chair-like conformation, and the central rings of p-iminobenzene moieties of the two molecules are severely twisted from the planarity of two dithiole rings, respectively. The UV–vis spectra of 1 and 2 show the lowest-energy absorption bands caused by the HOMO–LUMO one-electron promotion. Cyclic voltammetry (CV) measurements show only one, two-electron irreversible oxidation picks. These experimentally estimated energy levels of the frontier orbital of 1 and 2 (E HOMO 1: = −5.45, 2: −5.47 eV) are in good agreement with those obtained from DFT calculations (E HOMO 1: = −5.5, 2: = −5.3eV). The high HOMO–LUMO gaps of 1 (4.05eV) and 2 (4.00eV) indicate high kinetic stability of the title compounds.