Here we report our investigation of 1-bromo-3,5,7-triphenyladamantane (1) and the elucidation of polymorphic crystals (1A and 1B) using single crystal X-ray diffraction. In the monoclinic crystal system of 1A (P21/n), we observed CH−π interactions, while Br···Br interactions are absent. Conversely, the Br···Br interactions are an apparent factor in the formation of the monoclinic crystal system of 1B (R3). We compare our findings with 1,3,5,7-tetraphenyladamantane (2), characterized by numerous CH−π interactions in the solid. Computational analyses were employed to investigate the interactions within the characteristic dimers present in the unit cells of 1A and 1B, including visualization of noncovalent interactions and the use of the atoms-in-molecules approach, and MO analysis. These support the notion of London dispersion (LD) dimer-dimer interactions in 1A between the phenyl moieties, whereas 1B exhibits additional dimer-dimer Br···Br contacts. In contrast, the crystals of 2 are exclusively held together by CH−π stacking LD interactions, a feature absent in the polymorphs of 1. Both polymorphic forms of 1 emit white light when subjected to 900 nm continuous wave laser irradiation, displaying a subtle blue shift compared to 2. The absence of CH−π stacking interactions between the dimers of 1 causes a small red-shift in the emission spectrum.