Ionic liquids (ILs) containing cationic mixed-valence biferrocenylene derivatives were synthesized with an octanoyl or octyl substituent in each cation. Their melting points ranged between 25 and 39 °C, and the octanoyl derivatives exhibited higher melting points than the octyl derivatives. In addition, each IL exhibited a glass transition in the temperature ranging from -66 to -45 °C after melting. Their melting points were ∼10 °C higher than those of mononuclear octamethylferrocenium salts bearing the same substituents. The solvent polarity (ETN) and Kamlet-Taft parameters (π*, α, and β) of these dinuclear and mononuclear ILs were then examined. The dinuclear ILs bearing octanoyl substituents exhibited significant increases in ETN and π* and a decrease in α with the decreasing temperature, whereas the other ILs exhibited a significantly less pronounced temperature dependence. Finally, the intervalence charge-transfer (or charge-resonance) bands of the octanoyl dinuclear ILs exhibited red shifts with the decreasing temperature, which can be regarded as self-thermosolvatochromism.