The very first representative of trithia-bridged N-heterotriangulene, a triphenylamine with sulfur atoms bridging the ortho-positions, was synthesized by a sequence of regioselective sulfenylation with phthalimidesulfenyl chloride followed by Lewis acid-catalyzed electrophilic cyclization. X-ray crystallography revealed a saddle-shaped geometry of the polycyclic scaffold. UV/Vis absorption spectroscopy and cyclic voltammetry were used to characterize the optoelectronic properties. The title compound is a particularly strong electron donor forming a perfectly stable radical cation, which was analyzed by electron paramagnetic resonance spectroscopy and X-ray crystallography. The electron donor properties were further highlighted by the formation of crystalline donor-acceptor complexes with strong cyano-based acceptors.