AbstractFor the purposes of new membrane material development for pervaporation separation based on crosslinked polyvinyl alcohol (PVA), IR spectroscopy and DSC were used to characterize the crosslinking reaction and the imidization of the (PVA)‐amic acid system. The IR spectra and the thermal analysis were performed on specimens that had been reacted for several different times at 150°C. The crosslinking reaction between the hydroxy groups of PVA and the carboxylic groups of amic acid was faster than the imidization of the amic acid. The best reaction times were about 30 min for the crosslinking reaction and 90 min for the imidization. The effects of the reaction time and the amic acid content on the thermal and mechanical properties have also been investigat