Thermal curing of poly(4,4’-oxybis(phenylenepyromellitamic acid)) (PAA) films prepared from PAA solutions using a novel solvent system composed of tetrahydrofuran (THF) and methanol (MeOH) has been investigated. In the drying process of casted PAA films, MeOH was entirely evaporated, while a significant amount of THF remained in the dried film. The progress of thermal imidization was observed during the process of drying at 80 degrees C. NMR measurements for the dried film revealed that the thermal imidization of trans-amidized PAA predominated over that of cis-amidized PAA. Dynamic mechanical thermal analyses (DMTA) pointed out that the dried PAA film containing THF showed no significant plasticization during the thermal cure. This indicates the mobility of polymer chain would be low during the thermal cure so that the resulting polyimide film has a higher in-plane orientation. The coefficient of thermal expansion (CTE) of the polyimide film was found to be low compared with a film obtained from a PAA solution using NMP.