In the present paper new generation of imidazole-derived lithium salts (LiTDI—lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide, LiPDI—lithium 4,5-dicyano-2-(pentafluoroethyl)imidazolide and LiHDI—lithium 4,5-dicyano-2-(n-heptafluoropropyl)imidazolide) applied in a model liquid electrolyte, with propylene carbonate used as a solvent, is described. Room temperature ionic conductivities measured by Impedance Spectroscopy are as high as 10−2 to 10−3 Scm−1 for the 0.1–1moldm−3 salt concentration range. Lithium cation transference numbers calculated using the Bruce–Vincent method exceed 0.4 at salt concentration equal to 1moldm−3. Interface resistance measurements showed good stability at high—0.5moldm−3 or low—0.01moldm−3 salt concentrations. Ionic associations were estimated using Fuoss–Kraus semiempirical method revealing relatively low association rates. The effect of anion structure on ionic interactions and electrochemical characteristics of the studied electrolytes is discussed.