context: Herein, a Li/LiV2(PO4)3 primary battery (Fig. 1a) with a long shelf life is proposed, which exhibits impressive electrochemical performances under high power densities and low-temperature conditions. It has been found that the corrosion of the Al current collector triggered by the organic radical cations generated from the electrochemical oxidation of EC at high potentials; and the detrimental reaction between LiV2(PO4)3 and electrolyte lead to the self-discharge of Li/LiV2(PO4)3 primary batteries. When EC was replaced by PC, the corrosion of the Al foil was alleviated. LiBOB was found to be conducive to increase the shelf life of the Li/LiV2(PO4)3 primary batteries as it formed a protective film on the surface of the cathode, which effectively alleviated the side reaction between LiV2(PO4)3 and the electrolyte. Most importantly, the Li/LiV2(PO4)3 primary batteries exhibited excellent performances at high charge/discharge rates (up to 50C) and even at temperatures as low as −40 °C.