Carbon hollow fiber membrane derived from polyetherimide (PEI) blend with polyvinylpyrrolidone (PVP) was prepared by pyrolysis under air and N(2) environment. The characteristics of the carbon structures and the gas separation properties of carbon hollow fiber membranes pyrolyzed at different temperatures were studied. The prepared membranes were extensively characterized using thermogravimetry analysis, scanning electron microscopy, and X-ray diffraction for its morphology, thermal stability and structure properties, respectively. Pure gases of different molecular size (CO(2). N(2) and CH(4)) were used to determine the permeation properties of the carbon membrane. The permeance of the three gases decreased with increasing of pyrolysis temperature, however the selectivity of the gas pairs such as CO(2)/CH(4) and CO(2)/N(2) increased significantly. PEI/PVP is a promising carbon membrane precursor, which resulted in good separation performance for CO(2)/CH(4) and CO(2)/N(2). According to permeation data, it is confirm that the gas separation performance of prepared PEI/PVP-based carbon membranes significantly better than its polymer precursor. (C) 2011 Elsevier B.V. All rights reserved.