In this study, heat-treated polyacrylonitrile (PAN) hollow fiber membranes have been used to investigate the pervaporation performances of aqueous ethanol solution. The heat-treated PAN hollow fiber membranes were prepared by heat treating the as-spun PAN precursor hollow fiber membranes at 120,160 and 210 degrees C for 12 h under air atmosphere, respectively. Scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), simultaneous thermal analysis/mass spectrometry (TA/MS) and thermogravimetric analysis (TGA) are used to characterize the properties of hollow fiber membranes. The 90 wt.% aqueous ethanol solution at 25 degrees C has been used to investigate the pervaporation performances through hollow fiber membrane. Furthermore, in this investigation, we also use the positron annihilation spectroscopy (PAS) to identify the effect of heat-treatment on free volume variation of PAN hollow fiber membranes. To our knowledge, it is the pioneering work for PAS analysis technique used in hollow fiber membranes. The results have shown that the pervaporation performances of PAN hollow fiber membrane can be improved by heat-treatment. The permeation rate decreases while water content in permeate increases with increasing heat-treatment temperature. These phenomena might be due to that after heat-treating, the PAN hollow fiber membrane morphology becomes denser and the free volume of PAN polymer chain is reduced. Finally, heat-treated PAN/polyethylene glycol (PEG)10K blended hollow fiber membranes are also fabricated to investigate the pervaporation performance of aqueous ethanol solution. It has shown that the permeation rate as well as water content in permeate increases with increasing heat-treatment temperature. These phenomena can be interpreted that some of the PEG10K in hollow fiber membrane matrix has burnt away by heat-treating, and the occupied space of PEG10K would lead water molecules more easy to permeate. The long-term pervaporation stability of 210 degrees C heat-treated PAN hollow fiber membranes was also investigated in this study. It has shown that the long-term pervaporation stability can last at least 250 days. (C) 2010 Elsevier B.V. All rights reserved.