Room temperature phosphorescence from organic materials has attracted an increasing attention in the recent years due to their potential application in various advancing technologies, notably in bioimaging and displays. In this context, heavy atoms such as halogen ones revealed useful tools to enhance the spin‐orbit coupling (SOC) of molecular organic phosphors. However, the effect of halogen at the supramolecular level remains less understood, especially in the field of molecular crystals where additional factors can impact the phosphorescence emission. Here, we investigate external effect of halogens on the phosphorescence of chiral phthalimides molecular crystals. The results show that changing the nature of the halogen atom onto the phthalimide core leads to an evolution of the photophysical properties of the materials which does not necessarily follow the classical trend imposed by the expected internal heavy atom effect. Beyond this aspect, we showed that the halogen atom has a profound impact on the packing between the chromophores at the supramolecular level which is of paramount importance towards the optical properties (PLQY and lifetimes) of the different phosphors examined.