Organophosphorus(V) fluorides have a long and tumultuous history, with early applications as toxins and nerve agents reflecting their poisonous past. Behind these very real safety considerations, there is also growing potential in a wide range of fields, from chemical biology to drug development. The recent inclusion of organophosphorus(V) fluorides in click chemistry exemplifies the promise these compounds possess and brings these molecules to the brink of a resurgence. In this perspective, we delve into the history of phosphorus(V) fluoride (P(V)–F) compounds, discuss the precautions needed to work with them safely, and explore recent advancements in their synthesis and application. We conclude by discussing how this field can continue on a path toward innovation.

有机磷（V）氟化物有着悠久而动荡的历史，早期作为毒素和神经毒剂的应用反映了它们有毒的过去。在这些非常现实的安全考虑的背后，从化学生物学到药物开发等广泛领域也有不断增长的潜力。最近，有机磷（V）氟化物被纳入点击化学，这证明了这些化合物所具有的前景，并将这些分子带到了复兴的边缘。从这个角度来看，我们深入研究了氟化磷（V）（P（V）–F）化合物的历史，讨论了安全使用它们所需的预防措施，并探索了其合成和应用的最新进展。最后，我们讨论了该领域如何继续走上创新之路。