Photoluminescent compounds showing emission color changes in response to external stimuli have received considerable attention because of their wide range of applications. Here, we report the unique photoluminescence behavior of a digold(I) coordination system with trigonal-planar Au(I) centers, [Au2(dppm)3](2+) (dppm = bis(diphenylphosphino)methane). This system shows an extremely intense phosphorescence, with a quantum yield of >95% in the solid state. Both the emission color and thermal stability vary due to changing counter ions (Cl(-) vs. OTf(-)). Of particular note is the thermal crystalline-amorphous-crystalline transformation for the chloride salt, which is accompanied by drastic emission color changes. Single-crystal and powder X-ray diffractions demonstrate that the two-step transformation is induced by the loss of water molecules of crystallization with the subsequent removal of a dppm ligand to form [Au2(dppm)2](2+), which is mechanically reverted back to [Au2(dppm)3](2+).