Dynamically linked polymers (dynamers) have attracted attention as a versatilebuilding block for, e.g., self-healing polymers. However, research on combiningoptically active materials with dynamic chemistry is still in its infancy. Here, we reporton a highly emissive arylene ethynylene oligomer bearing a bis-furan functionalization,which makes it suitable for the utilization in Diels-Alder dynamers. By combiningsteady-state and time-resolved absorption and emission spectroscopy from the femtotothe nanosecond timescale, the molecular dynamics of the excited state of themonomeric building block and the corresponding Diels-Alder polymer have beeninvestigated in detail. While in solution, no pronounced differences in theirphotophysics were observed, thin films of the polymer exhibit a distinct dual emissionwith single chromophore and excimer character, respectively.