The effort to develop improved electrolytes that satisfy the requirements of lithium rechargeable batteries has intensified the search for new conducting salts having an improved chemical and electrochemical stability. With lithium fluoroalkylphosphates, we introduce a new class of conducting salts for electrolytes for high energy lithium-ion batteries. The results of electrochemical studies of Li[(C2F5)3PF3] in organic carbonates in comparison to LiPF6 including electrochemical stability and charge–discharge efficiency are reported. In addition, the influence of perfluorinated alkyl groups on stability towards hydrolysis is demonstrated.