The safe generation of F2 gas at room temperature by using simple cell configurations has been the “holy grail” of fluorine research for centuries. Thus, to address this issue, we report generation of F2 gas through the electrolysis of CuF2 in a CsF‐2.45HF molten salt without the evolution of H2 gas. The CuF2 is selected through a series of thermodynamic and kinetic assessments of possible metal fluorides. Anode assessments on graphite and glass‐like carbon demonstrate the effect of the absence of the anode during generation of F2 gas owing to stabilized operations at room temperature. Although the Ni anode dissolves during electrolysis in the conventional medium‐temperature cell, herein, it facilitates stable electrolysis over 100 h, achieving an F2 gas purity of over 99 % with the potential to operate using one‐compartment electrolysis. This work presents a safe and propitious method for the generation of high‐purity F2 gas for small‐scale lab and industrial applications.