Carbon hollow fiber membranes (CHFMs) derived from polymer blend of polyetherimide (PEI) and polyvinylpyrrolidone (PVP) were extensively prepared through stabilization under air atmosphere followed by carbonization under N-2 atmosphere. The effects of the stabilization temperature on the morphological structure, chemical structure, and gas permeation properties were investigated thoroughly by means of scanning electron microscopy, Fourier transform infrared spectroscopy, and single gas permeation system. The experiment results indicate that the transport mechanism of small gas molecules of N-2, CO2, and CH4 is dominated by the molecular sieving effect. Based on morphological structure and gas permeation properties, an optimum stabilization condition for the preparation of CHFM derived from PEI/PVP was found at 300 degrees C under air atmosphere. The selectivity of 55 and 41 for CO2/CH4 and CO2/N-2, respectively, were obtained for CHFMs prepared at stabilization temperature of 300 degrees C. (C) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 127: 2840-2846, 2013