The new binary mixed-valence fluoride of germanium, Ge₃F₈, has been obtained by heating GeF₄ with powdered Ge in an autoclave (390 K/4 bar/48 h). The structure contains pyramidal Ge^IIF₃ and octahedral Ge^IVF₆ units, linked by fluoride bridges. The new compound is the missing member of the series (GeF₂)_n·GeF₄ (n = 2, 4, or 6). Sublimation of (GeF₂)_n·GeF₄in vacuo provides a convenient source of GeF₂ in ca. 30% overall yield.