Three new series of mono- and bis-cyclic amidinium cations bearing alkyl chains of different length were synthesized. 53 salts were generated upon combining the cations with a variety of anions and their thermal behaviour was investigated. Depending on the structure and the charges state of the cyclic amidinium moiety and the nature of the anion, several of the obtained salts behaved as ionic liquids with their melting point in the range of ca. 25–94 °C.