AbstractMetal‐free organophosphorus are demanded compounds due to their interesting properties in a variety of applications, spanning from fine to material chemistry. Unfortunately, their synthesis is very challenging, requiring a precise design of the reaction conditions to avoid the conspicuous formation of undesired products. The P‐butterfly scaffold is considered the very first opening step of the white phosphorus tetrahedron upon selective cleavage of just one P−P bond. While the synthesis of metal‐containing P‐butterflies is nowadays reproducible with a variety of transition metal complexes, the metal‐free analogues are still elusive and just a limited number of examples is described in the literature. The state of art on known metal‐free phosphorus butterfly compounds is described herein.