The electroactive lithium vanadium fluorophosphate phase, LiVPO4F (P 1 ¯ , a =5.1687(2)Å, b =5.3062(2)Å, c =7.5031(3)Å, α =66.856(2)°, β =67.004(2)°, γ =81.583(2)° and cell volume=174.21(1)Å3) has been synthesized by a two-step reaction scheme based on a carbothermal reduction (CTR) process. High-resolution electrochemical measurements reveal a structured voltage response for the lithium extraction process while the lithium insertion process proceeds via a two-phase reaction mechanism centered at around 4.2V versus Li. Performance evaluation of a graphite||LiVPO4F lithium-ion cell indicates an average discharge voltage of 4.06V coupled to an initial material utilization for the LiVPO4F of around 123mAhg−1. Long-term cycling of this lithium-ion system demonstrates good capacity retention over the first 300 cycles. Based on the available data we believe the LiVPO4F offers considerable promise as a viable cathode replacement for LiCoO2.