In this work, samples of the δ-Bi2O3 phase are investigated. This phase is known as a solid electrolyte and has a very high ionic conductivity. The investigated structure formation is caused by synchrotron radiation (SR) directed to the surface of a δ-Bi2O3 crystal. SR differs from radiation received from other sources in its wide spectral range (from infrared to hard X-ray) and high intensity. Diffraction patterns obtained during the exposure process are decoded and studied in this work. The study reveals the polymorphism that forms a phase sample of δ-Bi2O3 under the action of SR as an example of a nonequilibrium transition. In complex compounds, the processes of redistribution of elements in the composition of microstructures are not yet understood due to the fact that radiation-enhanced phase formation is possible during irradiation. The texture found in the diffraction pattern can be explained as the result of the shock-wave load coming from the SR. This process arises from a collection of optical phonons with different wavelengths. Deformations of the crystal lattice are created under a strong electron-phonon interaction. It leads to a displacement of atoms which is recorded during the decoding of the diffraction patterns.