A series of ionic liquids containing cationic ruthenium complexes ([Ru(C5H5)(C6H5R)](+)) were prepared, and their thermal properties were investigated (R = C4H9 (1a), C8H17 (1b), OCH2OCH3 (2a), O(CH2CH2O)2CH3 (2b), O(CH2)3CN (3a), O(CH2)6CN (3b), CO(CH2)2CH3 (4a), CO(CH2)6CH3 (4b)). Bis(trifluoromethanesulfonyl)amide (TFSA) and bis(fluorosulfonyl)amide (FSA) were used as counter anions. These ionic liquids were colorless and stable toward air and light. These salts exhibited glass transitions upon cooling from the melt (Tg = −82 °C to −55 °C), and the glass transition temperatures of the salts increased as the polarity of the substituents increased (alkyl < ether < cyano < carbonyl). The decomposition temperatures decreased in the order of alkyl > cyano > carbonyl > ether. The viscosities, solvent polarities, and refractive indices of the salts of 1a and 2a were also evaluated. Hexafluorophosphate (PF6) salts were also prepared, which were solids with high melting points (Tm = 65–127 °C). X-ray crystal structure analyses of these salts revealed the importance of intermolecular contacts involving the ring hydrogens. The PF6 salt of 2a exhibited an order–disorder phase transition.