•Olefin separation by silver(I) ions in ionic liquids and polymeric ionic liquids.•Silver(I) based polymeric ionic liquid used as gas chromatographic stationary phase.•Chemical structure of ionic liquid affects interaction of silver(I) ion and olefin.•Two-dimensional gas chromatography enhanced olefin separation using silver(I) ion.•Polymeric structure in ionic liquid eased silver(I) reduction at high temperatures. Silver(I) ions have been used in various studies as components within polymer membranes or ionic liquids (ILs) to enable separation of olefins from paraffins. Polymeric ionic liquids (PILs) are a class of polymers synthesized from IL monomers and typically possess higher thermal and chemical stability than the ILs from which they are formed. Until now, very little is known about the difference in strength of silver(I) ion-olefin interactions when they take place in an IL compared to a PIL. In this work, the chromatographic separation of olefins by stationary phases composed of silver(I) bis(trifluoromethyl)sulfonylimide (Ag+NTf2−) incorporated into the 1-hexyl-3-methylimidazolium NTf2 (HMIM+NTf2−) IL and poly(1-hexyl-3-vinylimidazolium NTf2) (poly(HVIM+NTf2−)) PIL at varying concentrations was investigated. Olefins were more highly retained by silver(I) ions in PILs than in ILs as the silver(I) salt concentration in the stationary was increased. The potential separation power of silver(I)-containing IL and PIL stationary phases in comprehensive two-dimensional gas chromatography (GC×GC) was compared to the conventional one-dimensional system. The separation selectivity of alkenes and alkynes from paraffins was significantly increased, while dienes and aromatic compounds showed insignificant changes in retention. The chemical structural features of IL and PIL that enhance silver(I) ion stability and olefin separation were investigated by using silver(I) trifluoromethanesulfonate (Ag+OTf−), 1-decyl-3-methylimidazolium NTf2 (DMIM+NTf2−) IL, poly(1-decyl-3-vinylimidazolium NTf2 (poly(DVIM+NTf2−)) PIL, HMIM+OTf− IL and poly(HVIM+OTf−) PIL. Longer alkyl substituents appended to the IL (and PIL) cation increased the strength of silver(I) olefin interaction, and OTf− anions in the IL (and PIL) tended to preserve silver(I) ion from thermal reduction, while also retaining olefins less than the NTf2−-containing columns. In general, silver(I) ions in PILs possessing analogous chemical structures to ILs exhibited higher silver(I) ion-olefin interaction strength but were less thermally stable.