Black phosphorus was compressed at room temperature across the A17, A7 and simple‐cubic phases up to 30 GPa, using a diamond anvil cell and He as pressure transmitting medium. Synchrotron X‐ray diffraction showed the persistence of two previously unreported peaks related to the A7 structure in the pressure range of the simple‐cubic phase. The Rietveld refinement of the data demonstrates the occurrence of a two‐step mechanism for the A7 to simple‐cubic phase transition, indicating the existence of an intermediate pseudo simple‐cubic structure. From a chemical point of view this study represents a deep insight on the mechanism of interlayer bond formation during the transformation from the layered A7 to the non‐layered simple‐cubic phase of phosphorus, opening new perspectives for the design, synthesis and stabilization of phosphorene‐based systems. As superconductivity is concerned, a new experimental evidence to explain the anomalous pressure behavior of Tc in phosphorus below 30 GPa is provided.