Drying and imidization of PMDA-ODA solutions in NMP were investigated by a novel custom designed measurement system that tracks real time weight, thickness, surface temperature, and in-plane and out-of-plane birefringence. At low temperature drying stage, the weight and thickness reductions occurred rapidly as a result of solvent evaporation. All the parameters started leveling off while the out of plane birefringence steadily increased and reached a plateau at longer drying times. When the temperature was increased for imidization reaction, additional weight loss accompanied by temporary reduction of birefringence was observed due to evaporation of bound solvent as solvent molecules decomplexed from the polymer chains and plasticized the film. During the latter stage, out-of-plane birefringence rose rapidly due to increased intrinsic birefringence of the polymer chains due to imidization reaction and orientation of polymer chains with their chain axes preferentially oriented in the film plane. Throughout the whole process the in-plane birefringence remained zero. For the first time, these real time measurements allowed us to quantitatively show the dynamics between chain relaxation due to evaporation of the decomplexed solvent molecules, and orientation development due to decreased chain mobility caused by imidization reaction and increasing T-g for the PMDA-ODA/NMP solutions. In addition, the dynamics of this interplay was investigated by varying the processing conditions: initial casting thickness and drying temperature.