Fused donor–acceptor triads composed of two tetrathiafulvalenes (TTFs) and benzoquinone (BQ; 1) or naphthoquinone (NQ; 2) were successfully synthesized. X‐ray structure analysis of the bis(n‐butylthio) derivative revealed that the molecules are stacked in a head‐to‐tail manner. The bis(n‐hexylthio)‐1 exhibited six‐pairs of one‐electron transfer waves in the cyclic voltammogram, corresponding to the formation of both reduction and oxidation states from −2 to +4. The unsubstituted and bis(methylthio) derivatives of 1 and 2 were active materials in positive electrodes for rechargeable batteries, several of which displayed energy densities exceeding 800 mWh g−1. The bis(methylthio)‐2 also functions as a positive electrode material for a rechargeable sodium‐ion battery.

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