Sulfolane (also referred to as tetramethylene sulfone, TMS) containing LiPF6 and vinylene carbonate (VC) was tested as a non-flammable electrolyte for a graphite |LiFePO4 lithium-ion battery. Charging/discharging capacity of the LiFePO4 electrode was ca. 150mAhg−1 (VC content 5wt%). The capacity of the graphite electrode after 10 cycles establishes at the level of ca. 350mAhg−1 (C/10 rate). In the case of the full graphite |1M LiPF6 +TMS+VC 10wt% |LiFePO4 cell, both charging and discharging capacity (referred to cathode mass) stabilized at a value of ca. 120mAhg−1. Exchange current density for Li+ reduction on metallic lithium, estimated from electrochemical impedance spectroscopy (EIS) experiments, was j o(Li/Li+)=8.15×10−4 Acm−2. Moreover, EIS suggests formation of the solid electrolyte interface (SEI) on lithium, lithiated graphite and LiFePO4 electrodes, protecting them from further corrosion in contact with the liquid electrolyte. Scanning electron microscopy (SEM) images of pristine electrodes and those taken after electrochemical cycling showed changes which may be interpreted as a result of SEI formation. No graphite exfoliation was observed. The main decomposition peak of the LiPF6 +TMS+VC electrolyte (TG/DTA experiment) was present at ca. 275°C. The LiFePO4(solid)+1M LiPF6 +TMS+10wt% VC system shows a flash point of ca. 150°C. This was much higher in comparison to that characteristic of a classical LiFePO4 (solid)+1M LiPF6 +50wt% EC+50wt% DMC system (T f ≈37°C).