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Scintillators are essential in converting ionizing X‐rays and γ‐rays into visible light, with applications in medical diagnosis, security inspection, and non‐invasive detection. However, current scintillating materials exhibit unclear structure–function relationships. The performance of scintillators is intricately linked to their electronic band structure, particularly the intrinsic properties of excited states. Therefore, investigating the structural factors affecting scintillation performance is crucial for developing new scintillators. Therefore, Ba‐SMOF 1 ([Ba2(PyTS)(CH3OH)2(H2O)4]n) is synthesized using a pyrene‐based organic motif and metal Ba(II) ions, where PyTS4− refers to pyrene‐1,3,6,8‐tetrasulfonate. For the first time, the excited state of a pyrene‐based X‐ray scintillating metal–organic framework (MOF) is determined through comprehensive all‐electron excitation studies, including in situ experimental electron density and wave‐function analysis. The electron density maps exhibit a continuous overlap, attributed to the associative exciton behaviors among the closely packed PyTS4− linkers. These linkers are identified as the sources of both static and dynamic excimer emissions. The electron density studies reveal the role of excimers in pyrene‐based luminophores, highlighting that interchromophoric interactions are key to enhancing the performance of scintillating MOFs. This discovery opens new avenues for the practical application of scintillating MOFs. [ABSTRACT FROM AUTHOR]