We report on the solid‐state structures of bis(nonafluoro‐tert‐butyl) peroxide [(F₃C)₃CO]₂ and bis(undecafluoro‐2‐methyl‐2‐butyl) peroxide [(C₂F₅)(F₃C)₂CO]₂. These peroxides were prepared from the corresponding hypofluorites and fluorinated silver wool. The solid‐state structures obtained after in situ crystallisation show unusual COOC dihedral angles of 180°, as well as elongated O−O bonds because of the bulky perfluorinated alkyl groups. The perfluorinated alkyl peroxides are insensitive to both impact (>40 J) and friction (>360 N), and resistant towards mineral acids (HX; X=F, Cl, Br) and elemental halogens (X₂). Ferrocene is oxidized by [(F₃C)₃CO]₂ to [FeᴵᴵᴵCp₂][OC(CF₃)₃].