The phase stability of γ‐P3N5 and the possible formation of new phosphorus nitrides were investigated via high‐pressure in situ Raman spectroscopy, X‐ray diffraction measurements, and first‐principles calculations up to approximately 80 GPa. In this study, γ‐P3N5 was synthesized via the direct nitridation of black phosphorus at a pressure approximately above 12 GPa. The Raman spectrum, bulk modulus (K0 = 130.27(43) GPa), and compression behaviors (order of axial compressibility: βc > βa > βb) were experimentally measured for the first time. These experimental results were in good agreement with those of first‐principles calculations. Our high‐pressure in situ measurements and first‐principles calculations revealed that γ‐P3N5 persisted up to 80 GPa at room temperature. The compression of γ‐P3N5 proceeded with the folding of the layer consisting of the corner‐ and edge‐sharing PN4 and PN5. The present findings indicate that the P–N bonding with a low coordination number (PN4 and PN5) is preferable and stabilized for phosphorus nitride over a wide pressure range. However, laser heating between 67 and 70 GPa in the presence of nitrogen resulted in the formation of new PxNy, which included the possibility of a new high‐pressure P3N5 phase. The Raman scattering measurements along with the decompression demonstrated that the local structure of the newly synthesized PxNy metastably persisted at atmospheric pressure. The present experimental and theoretical studies on phosphorus nitrides offer new insights into the high‐pressure behaviors of covalent compounds consisting of highly coordinated polyhedra.