Materials that once suffered under high-pressure and high-temperature conditions often display unusual phenomena that challenge traditional understanding. MnF 3 , an intermediate valence state Mn-F compound, exhibits a distorted octahedral crystal structure influenced by the Jahn-Teller effect. Here we report the structural phase transition and self-disproportionation of MnF 3 under high pressure and high temperature. The initial octahedra phase I 2/ a -MnF 3 transforms into the hendecahedra Pnma phase under high pressure. Subsequently, we found that molten Pnma -MnF 3 self-disproportionate into MnF 2 and MnF 4 with the aid of laser heating at a pressure above 57.1 GPa. Raman spectra and UV-vis absorption experiments confirmed these changes that were ultimately confirmed by synchrotron radiation XRD. The equation of states for the volume with the pressure of these Mn-F compounds was also given. This work expands the study of Mn-F systems and provides guidance for the behavior of transition metal fluorides under high pressures and high temperatures.