Four metal-organic frameworks with similar topology but different chemical environment inside the pore structure, namely, IFP-1, IFP-3, IFP-5, and IFP-7, have been investigated with respect to the separation potential for olefin-paraffin mixtures as well as the influence of the different linkers on adsorption properties using experiments and Monte Carlo simulations. All IFP structures show a higher adsorption of ethane compared to ethene with the exception of IFP-7 which shows no selectivity in breakthrough experiments. For propane/propane separation, all adsorbents show a higher adsorption for the olefin. The experimental results agree quite well with the simulated values except for the IFP-7, which is presumably due to the flexibility of the structure. Moreover, the experimental and simulated isotherms were confirmed with breakthrough experiments that render IFP-1, IFP-3, and IFP-5 as suitable for the purification of ethene from ethane.