This work reports the adsorption and coadsorption data of CO2/CH4/CO mixtures on several metal–organic frameworks [MOFs; MIL-100(Cr), MIL-47(V), MIL-140(Zr)-A, Cu-btc, and MIL-53(Cr)] and compares them with reference adsorbents, that is, zeolite NaX and an activated carbon material, AC35. We also evaluate the effect of H2O on CO2 adsorption and on the stability of the structures. Based on the experimental adsorption data, the performance potential of MOFs in several pressure swing adsorption processes is estimated by making a ranking of working capacities and separation factors. We discuss the separation of biogas, the purification of H2 produced by steam reforming of methane, and the removal of CO2 from synthesis gas in IGCC (integrated gasification combined cycle) systems. Some MOFs are very well placed in the ranking of (isothermal) working capacity vs. selectivity. Yet, performance is not the only criterion for the selection of MOFs. Ease and cost of synthesis and long-term stability are other important aspects that have to be taken into account.