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Positively polarized gold nanoparticles have been demonstrated for use as stable olefin carriers for facilitated olefin transport membranes. The formation and size of gold nanoparticles stabilized by 4-dimethylaminopyridine (DMAP) were monitored using X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV–visible spectroscopy. Nanocomposite membranes that deliver high separation performance for olefin/paraffin mixtures were prepared by dispersing gold nanoparticles stabilized by DMAP in a polymer matrix, poly(vinyl pyrrolidone) (PVP). X-ray photoelectron spectroscopy (XPS) and zeta potential measurements revealed that gold nanoparticles stabilized by DMAP exhibited a high positive polarity, which is responsible for the reversible interaction between the gold nanoparticles and olefin molecules. Compared to neat PVP membranes, the composite membranes consisting of PVP and the polarized gold nanoparticles showed stable and enhanced separation of olefin/paraffin mixtures. ; This work was supported by Energy Technology R&D program (2006-E-ID11-P-13) under the Korea Ministry of Commerce, Industry and Energy (MOCIE). KC acknowledges the financial support of NSI-NCRC and the Ministry of Education through the Brain Korea 21 Program at Seoul National University. This work was also supported by ERC Program of KOSEF grant funded by the Korea government(MEST) (R11-2005-048-00000-0).