In this study, the conformational variety of the pyrene excimer in solution has been thoroughly investigated. Several minimum-energy arrangements of the constituent monomers were obtained, representing the closest accessible relaxed conformations for the as-formed aggregate in its first excited state. Additionally, we shed light on the conformational dynamics connecting different stable structures, estimating energy barriers and the associated reaction times. This ultimately revealed an overall flow to the most stable conformer, whose fluorescent behavior is predicted in excellent agreement with both static and time-dependent experimental results obtained under comparable conditions. As such, the typical excimer emission can be regarded as the downstream result of a complex kinetic scheme with competing relaxation and structural reorganization channels. Our findings contribute to improving our understanding of this well-known, yet still elusive, species, bridging the gap between available pieces of evidence at both theoretical and experimental levels.