New cyclic quaternary ammonium salts, composed of N-alkyl(alkyl ether)-N-methylpyrrolidinium, -oxazolidinium, -piperidinium, or -morpholinium cations (alkyl=nC4H9, alkyl ether=CH3OCH2, CH3OCH2CH2) and a perfluoroalkyltrifluoroborate anion ([RFBF3]−, RF=CF3, C2F5, nC3F7, nC4F9), were synthesized and characterized. Most of these salts are liquids at room temperature. The key properties of these salts—phase transitions, thermal stability, density, viscosity, conductivity, and electrochemical windows—were measured and compared to those of their corresponding [BF4]− and [(CF3SO2)2N]− salts. The structural effect on all the above properties was intensively studied in terms of the identity of the cation and anion, variation of the side chain in the cation (i.e., alkyl versus alkyl ether), and change in the length of the perfluoroalkyl group (RF) in the [RFBF3]− ion. The reduction of Li+ ions and reoxidation of Li metal took place in pure N-butyl-N-methylpyrrolidinium pentafluoroethyltrifluoroborate as the supporting electrolyte. Such comprehensive studies enhance the knowledge necessary to design and optimize ionic liquids for many applications, including electrolytes. Some of these new salts show desirable properties, including low melting points, high thermal stabilities, low viscosities, high conductivities, and wide electrochemical windows, and may thus be potential candidates for use as electrolytes in high-energy storage devices. In addition, many salts are ionic plastic crystals.