Novel inorganic-organic membranes that contained Ag+ ions as olefin carriers were prepared using sol-gel and dip-coating processes. The permeance of the membranes for nitrogen, helium, ethane (C2H6), and ethene (C2H4) were evaluated using the single-gas permeation method at temperatures of 298, 373, and 423 K. The results showed that the selectivity of the membranes to C2H4 against C2H6 increased as the measurement temperature increased, because the decomplexation rate of C2H4 molecules from Ag+ sites is enhanced by increases in the temperature. Fourier transform infrared spectrophotometry of the hybrid membranes and the performance of the membranes at 373 and 423 K indicated that poly(N-vinylpyrrolidone) (PVP) had a role in increasing the flexibility of the inorganic network and also served as a mediation agent to fix Ag+ ions in the polymer segments, because of the coordination interaction between the Ag+ ions and the PVP.