A series of hydrophobic room temperature ionic liquids (ILs) based on ethereal functionalised pyrrolidinium, piperidinium and azepanium cations bearing the bis[(trifluoromethyl)sulfonyl]imide, [TFSI]−, anion were synthesized and characterized. Their physicochemical properties such as density, viscosity and electrolytic conductivity, and thermal properties including phase transition behaviour and decomposition temperature have been measured. All of the ILs showed low melting point, low viscosity and good conductivity and the latter properties have been discussed in terms of the IL fragility, an important electrolyte feature of the transport properties of glass‐forming ILs. Furthermore, the studied [TFSI]−‐based ILs generally exhibit good electrochemical stabilities and, by coupling electrochemical experiments and DFT calculations, the effect of ether functionalisation at the IL cation on the electrochemical stability of the IL is discussed. Preliminary investigations into the Li‐redox chemistry at a Cu working electrode are also reported as a function of ether‐functionality within the pyrrolidinium‐based IL family. Overall, the results show that these ionic liquids are suitable for electrochemical devices such as battery systems, fuel cells or supercapacitors.