We propose lithium metal cells employing LiCF3SO3-tetraethylene glycol dimethy ether (TEGDME) electrolyte solution with LiFePO4 and LiMn0.5Fe0.5PO4 cathodes. The electrolyte is selected due to its non-flammability, herein demonstrated, and considered as a key requirement for application cells employing high energy lithium metal anode. The selected olivine cathodes, i.e., stable materials prepared by solvothermal pathway, have regular submicrometrical morphology suitable for cell operation and homogeneous composition, as confirmed by electron microscopy and energy dispersive X-ray spectroscopy. The electrochemical tests reveal promising cycling performances in terms of delivered capacity, stability and rate capability. The Li/LiCF3SO3-TEGDME/LiFePO4 cell operates at 3.5 V with capacity ranging from 150 mAh g−1 at C/10 to 110 mAh g−1 at 2C, while the Li/LiCF3SO3-TEGDME/LiFe0.5Mn0.5PO4 cell performs following two plateaus at 4.1 V and 3.5 V with capacity ranging from 160 mAh g−1 at C/10 to 75 mAh g−1 at 2C. Hence, the results demonstrate the suitability of TEGDME-based electrolytes in combination with LiFePO4 and LiFe0.5Mn0.5PO4 cathodes for high performances lithium battery.