Five new n‐tetrabutylphosphonium (P4444)+ cation‐based ionic liquids (ILs) with oligoether substituted aromatic carboxylate anions have been synthesized. The nature and position of the oligoether chain affect thermal stability (up to 330 °C), phase behaviour (Tg<−55 °C) and ion transport. Furthermore, with the aim of application in lithium batteries, electrolytes were created for two of the ILs by 10 mol% doping using the corresponding Li‐salts. This affects the ion diffusion negatively, from being higher and equal for cations and anions to lower for all ions and unequal. This is due to the stronger ionic interactions and formation of aggregates, primarily between the Li+ ions and the carboxylate group of the anions. Electrochemically, the electrolytes have electrochemical stability windows up to 3.5 V, giving some promise for battery application.