Stress relaxation following deformation of an entangled polymeric liquid is thought to be affected by transient reforming of chain entanglements. In this work, we use single molecule techniques to study the relaxation of individual polymers in the transition regime from unentangled to entangled solutions. Our results reveal the emergence of dynamic heterogeneity underlying polymer relaxation behavior, including distinct molecular subpopulations described by a single-mode and a double-mode exponential relaxation process. The slower double-mode timescale τ_{d,2} is consistent with a characteristic reptation time, whereas the single-mode timescale τ_{s} and the fast double-mode timescale τ_{d,1} are attributed to local regions of transient disentanglement due to deformation.