Pentafluorosulfanyl group is known as an emerging fluorinated group, it has been reported for the first time in 1960, and then remained an exotic fluorinated group for years, but nowadays this group is rising in interest and many groups and companies start to investigate this fluorinated motif in more depth. Indeed, SF5 is known as a “super CF3”, gathering and magnifying the benefits of CF3 that are a large volume, a high electronegativity and a high lipophilicity, which are highly valuable properties for drugs development. In parallel, a few applications of SF5-containing molecules has begun to appear in materials science, drug design or crop protection, but innovation remains highly dependent on the synthetic methods available to introduce SF5 in organic molecules. In this report, we turned our attention more specifically to SF5-alkynes, from their synthesis to applications.