The ionic conductivity pattern of LiTFSI/poly (oxypropylene) complexes is investigated. Contrarily to previous data, related to several lithium salt complexes, LiTFSI appears soluble in quite high concentration in PPO. The ionic conductivities are increased by more than one order of magnitude with respect to the more conductive compositions of PPO/CF3SO3Li, Nevertheless, despite the good solubility of LiTFSI in this host polymer, a partial salt precipitation is observed for the more concentrated sample.