In this paper, polyvinyl alcohol (PVA) membranes impregnated with amines (monoethanolamine and diethanolamine) were prepared for CO2/N2 separation. The cross-linking of DEA impregnated PVA by glutaraldehyde (GA) with different mass ratios (GA/PVA: 0.5, 1, 3, 5, 7%) were investigated with no use of acid catalyst or organic solvents. The effects of the amine type-concentration, cross-linking agent content, and feed pressure as well as stability were examined in both pure and mixed gases. Generally, CO2/N2 performance through the DEA-PVA membranes was higher than that of MEA-PVA membranes. The fabricated membranes were characterized by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The cross-linked membranes showed reasonable CO2/N2 permselectivities in comparison with uncross-linked membranes and these are recommended for high performance membrane for CO2/N2 separation. The best-yielding membranes (DEA-PVA/GA(1 wt%)/PTFE) represented the greatest CO2/N2 selectivity of 122.04 and 907.06 for pure and mixed gas experiments, respectively.