Abstract Multiple overlapping physical and chemical changes often take place during casting/drying and imidization from PMDA-ODA polyamic acid precursors from cast solutions. To shed light into details of these complex phenomena, we designed a unique real time measurement system that combines true stress, true strain, in-plane birefringence and temperature with polarized ultra-rapid scan FT-IR spectrometry (URS-FT-IR). At the early stages of heating (21°C–130 °C), initially isotropic solution cast film was observed to develop stress and birefringence as the solvent decomplexed and evaporated without showing any imidization as it was held in uniaxially constrained state. At a temperature around 130 °C, the onset of imidization reaction was detected while the stress went through a maximum. Beyond this stage, the evaporation of bound solvent and chemical conversion was observed to take place simultaneously and this is accompanied by a steady increase in birefringence. As the majority of the bound solvent evaporated, the stress and birefringence values started leveling off at long times.