Among ionic liquids, phosphonium-based ionic liquids (PILs) are quite elegant. These categories of ionic liquids represent some merits over other types of ionic liquids such as imidazolium- and pyridinium-based ionic liquids. PILs have more thermal and chemical stability than other reported ILs. These influential characteristics connected with PILs make them as potential structures for varied applications in academic and industrial processes. In recent years, however, PILs become popular because of relatively low cost of their synthesis (the rate of phosphonium salt formation is faster than those of nitrogen-based salts, implying higher productivity and lower cost in industrial manufacturing of PILs) as well as their good thermal stability, beneficial for high-temperature operation. Room temperature ionic liquids (RTILs) have numbers of unique applications in electrochemical systems and among them, phosphonium room temperature ionic liquids (PRTILs) have been increasing for their considerable advantages such as chemical and thermal stabilities, relatively low viscosities and high conductivities when compared to the corresponding ammonium RTILs. PRTILs are yummy electrolysis solutions because of their wide electrochemical window. Determination of the electrochemical stability of the PRTILs is important for detection and application of these ionic salts as electrolytes in electrochemistry. In order to evaluate electrochemical stability of the phosphonium RTILs, various voltammetric techniques such as cyclic voltammetry, linear sweep voltammetry and square wave voltammetry have been used. PRTILs characterized by a wide electrochemical window have been regarded as attractive candidates for lithium-battery electrolytes because of their stability and safety aspects. Contrary to what is seen in conventional organic solvents, superoxide is stable in ionic liquids. PILs are an unprecedented class of electrolytes that can support the electrochemical generation of a stable sup