Electrochemical oxidation of a catechol-fused tetraselenaful-valene (TSF) derivative unexpectedly gave its ortho-benzoquinone analogue, in contrast to the tetrathiafulvalene (TTF) system that afforded a hydrogen-bonded organic conductor. The obtained donor-acceptor dyad showed amphoteric redox character, a small HOMO-LUMO gap, effective intermolecular interactions, and NIR absorption.