This paper describes the extraction of C5-C8 linear alpha-olefins from olefin/paraffin mixtures of the same carbon number using silver(I)/N,N-dimethylbenzamide bis(trifluoromethylsulfonyl)imide ([Ag(DMBA)(2)][Tf2N]) or silver(I)/propylamine bis(trifluoromethylsulfonyl)imide ([Ag(PrNH2)(2)][Tf2N]) as the extracting agent. The separation performance of the system increased with increasing chain length. [Ag(DMBA)(2)][Tf2N] appeared to outperform [Ag(PrNH2)(2)][Tf2N] in terms of both selectivity and distribution coefficient. The [Ag(DMBA)(2)][Tf2N] system was successfully modeled using the universal quasi-chemical activity coefficient (UNIQUAC) model. These results support the potential future development of amine/amide-based ligands for producing soluble silver complexes useful for the separation of olefins from paraffins.