An in-depth study of mechanochromic and thermochromic luminescent copper iodide clusters exhibiting structural polymorphism is reported and gives new insights into the origin of the mechanochromic luminescence properties. The two different crystalline polymorphs exhibit distinct luminescence properties with one being green emissive and the other one being yellow emissive. Upon mechanical grinding, only one of the polymorphs exhibits great modification of its emission from green to yellow. Interestingly, the photophysical properties of the resulting partially amorphous crushed compound are closed to those of the other yellow polymorph. Comparative structural and optical analyses of the different phases including a solution of clusters permit us to establish a correlation between the Cu-Cu bond distances and the luminescence properties. In addition, the local structure of the [Cu4I4P4] cluster cores has been probed by (31)P and (65)Cu solid-state NMR analysis, which readily indicates that the grinding process modifies the phosphorus and copper atoms environments. The mechanochromic phenomenon is thus explained by the disruption of the crystal packing within intermolecular interactions inducing shortening of the Cu-Cu bond distances in the [Cu4I4] cluster core and eventually modification of the emissive state. These results definitely establish the role of cuprophilic interactions in the mechanochromism of copper iodide clusters. More generally, this study constitutes a step further into the understanding of the mechanism involved in the mechanochromic luminescent properties of metal-based compounds.