Organic molecules with fluoroalkylene scaffolds, especially a tetrafluoroethylene (CF2CF2) moiety, in their molecular structures exhibit unique biological activities, or can be applied to functional materials such as liquid crystals and light‐emitting materials. Although several methods for the syntheses of CF2CF2‐containing organic molecules have been reported to date, they have been limited to methods using explosives and fluorinating agents. Therefore, there is an urgent need to develop simple and efficient approaches to synthesize CF2CF2‐containing organic molecules from readily available fluorinated substrates using carbon‐carbon bond formation reactions. This personal account summarizes the simple and efficient transformation of functional groups at both ends of 4‐bromo‐3,3,4,4‐tetrafluorobut‐1‐ene and discusses its synthetic applications to biologically active fluorinated sugars and functional materials, such as liquid crystals and light‐emitting molecules.