AbstractThis work presents a joint theoretical and experimental characterisation of the structural and electronic properties of two tetrathiafulvalene (TTF)‐based acceptor–donor–acceptor triads (BQ–TTF–BQ and BTCNQ–TTF—BTCNQ; BQ is naphthoquinone and BTCNQ is benzotetracyano‐p‐quinodimethane) in their neutral and reduced states. The study is performed with the use of electrochemical, electron paramagnetic resonance (EPR), and UV/Vis/NIR spectroelectrochemical techniques guided by quantum‐chemical calculations. Emphasis is placed on the mixed‐valence properties of both triads in their radical anion states. The electrochemical and EPR results reveal that both BQ–TTF–BQ and BTCNQ–TTF–BTCNQ triads in their radical anion states behave as class‐II mixed‐valence compounds with significant electronic communication between the acceptor moieties. Density functional theory calculations (BLYP35/cc‐pVTZ), taking into account the solvent effects, predict charge‐localised species (BQ.−–TTF–BQ and BTCNQ.−–TTF–BTCNQ) as the most stable structures for the radical anion states of both triads. A stronger localisation is found both experimentally and theoretically for the BTCNQ–TTF–BTCNQ anion, in accordance with the more electron‐withdrawing character of the BTCNQ acceptor. CASSCF/CASPT2 calculations suggest that the low‐energy, broad absorption bands observed experimentally for the BQ–TTF–BQ and BTCNQ–TTF–BTCNQ radical anions are associated with the intervalence charge transfer (IV‐CT) electronic transition and two nearby donor‐to‐acceptor CT excitations. The study highlights the molecular efficiency of the electron‐donor TTF unit as a molecular wire connecting two acceptor redox centres.