A fluorinated carbonate (4‐(2,2,3,3,4,4,5,5,5‐nonafluoro‐pentyl)‐1,3‐dioxolan‐2‐one, 1) was synthesized from the corresponding oxirane through a one‐step carbonation reaction. The compound was obtained in quantitative yield with battery‐grade purity on a 50 g scale. Carbonate 1 was fully characterized by NMR, IR, MS, and crystal structure analysis. The compound melts at 98 °C and decomposes at 168 °C. When used as additive in lithium‐ion half‐ and full‐cell tests, 1 exhibited no reactivity toward the graphite anode, no participation in the solid‐electrolyte interphase (SEI) formation and led to a higher oxidation stability of the electrolyte against a carbon black electrode, compared to 4‐fluoro‐ethylenecarbonate and 4‐trifluoromethyl‐1,3‐dioxolan‐2‐one. The facile, clean, and scalable one‐step synthesis of 1 combined with its electrochemical behavior characterizes it as a promising additive for high voltage applications in lithium‐ion batteries.