Phosphorescence from pyrene especially at room temperature is uncommon. This emission was recorded utilizing a supramolecular organic host and the effect due to the heavy atom. Poor intersystem crossing from S-1 to T-1, small radiative rate constant from T-1, and large rate constant for oxygen quenching hinder the phosphorescence of aromatic molecules at room temperature in solution. In this study, these limitations are overcome by encapsulating a pyrene molecule within a water-soluble capsule (octa acid, OA) and purging with xenon. While OA suppressed oxygen quenching, xenon enabled the intersystem crossing from S-1 to T-1 and radiative process from T-1 to S-0 through the well-known heavy atom effect. The close interaction facilitated between the pyrene and the heavy atom perturber xenon in the three-component supramolecular assembly (OA, pyrene, and xenon) resulted in phosphorescence from pyrene. Computational modeling and NMR studies supported the postulate that pyrene and more than one molecule of xenon are present within a confined space of the OA capsule.