Аннотация:Due to their large bandgaps, multiferroic oxides, the promising candidates for overcoming the disadvantages of metal-halide perovskites as light absorbers, have so far very limited use in solar cell applications. Previous investigations demonstrate that high pressure represents an efficient tool for tuning the bandgap of multiferroic Mn3TeO6 (MTO). However, the underlying mechanism of the giant bandgap reduction discovered in MTO remains unclear, which critically prevents the design of next-generation light absorbers. In this study, we performed in situ x-ray diffraction analyses on the structure evolution of MTO upon compression and decompression, discovering a sequence of irreversible phase transitions R3⎯⎯→C2/c→P21/n. The experimental results, supported by electronic structure calculations, show the shortening of Mn–O–Mn bonding, and, to a lower extent, the decrease in connectivity of octahedra across the phase transition, explain the giant bandgap reduction of MTO. These findings will facilitate the design and synthesis of next-generation light absorbers in solar cells.We acknowledge support from the National Natural Science Foundation of China (Grant Nos. 12174356 and 11872056) and the Foundation of National Key Laboratory of Shock Wave and Detonation Physics of China (No. JCKYS2021212002). This research was also supported by Uppsala University.