In recent years, the use of natural compounds has gained much attention due to their low toxicity and wide availability. This work focused on using oleic acid (OA) as a widely available natural compound for synthesizing two new ionic liquids (ILs) and applying them to break water-in-oil (W/O) emulsions. For that, OA was epoxi-dized by m-chloroperbenzoic acid (mCPBA) to yield epoxidized oleic acid (EOA). Following this, amines, either pentaethylenhexamine, or tetraethylenepentamine, were reacted with EOA, yielding the corresponding ILs, EAPA-IL, and EATA-IL. Several techniques were used to characterize EAPA-IL and EATA-IL. Furthermore, the performance of EAPA-IL and EATA-IL for breaking W/O emulsion was examined. The factors affecting breaking these emulsions, including water ratio and demulsifier concentration, were studied. EAPA-IL and EATA-IL achieved efficient performance, reaching 100% at several demulsifier concentrations. The data showed that the performance increased as their concentration increased with time. Furthermore, EAPA-IL and EATA-IL separated clean water.