While dynamics of single-molecule (SM) fluorescent probes have been used to investigate the structure and relaxation processes in polymers near the glass transition temperature (T-g), it is difficult to perform SM imaging at elevated temperatures which restricts such studies to a limited number of polymers for which T-g is close to room temperature (RT). Plasticization, solvent (or additive) induced lowering of T-g, offers an alternate avenue to access various effective temperatures in the glassy and rubbery phases of polymers under ambient conditions. By investigation of the reorientational propensity of individual Rhodamine 6G (Rh6G) probes, which is governed by rigidity/dynamics of the polymer cavities, we have explored the extent of spatiotemporal heterogeneity during moisture induced plasticization of poly(vinylpyrrolidone) (PVP), far below and near (below and above) bulk T-g. Lack of any probe reorientation suggests that the matrix remains extremely rigid up to a certain level of hydration, as expected for probes buried deep within the glassy state. At intermediate levels of hydration, SMs undergo a wide variety of rotational dynamics ranging from being static/wobbling motion to slow, hindered large-angle reorientation, as well as facile, intermittently hindered fast rotation, which reflects that swelling/softening of network cavities is spatiotemporally extremely diverse as the effective T-g approaches RT. SM probes exhibit temporally nonuniform rotational mobility even at relatively high moisture contents of the matrix beyond which probes can undergo translational motion, which indicates that relatively slow time scale polymer segmental motion can be operational for plasticized PVP (in the rubbery state). Our inferences are supported by the non-Gaussian nature of angular jump distributions for dipolar reorientation, similar to those reported for translational diffusion of SM tracers in polymers and cellular media, suggesting the existence of slow time-varying local environmental changes around individual probe molecules during plasticization.