In this work, the effect of temperature on adsorption of CO2, CH4, CO, and N-2 and separation of their binary mixtures in ZIF-8 were investigated using experimental measurements combining with molecular simulations. The results show that for pure gas adsorption, the effect of temperature is large when strong adsorption occurs, mainly due to the variation of the interaction energy between adsorbate molecules with temperature; while for gas mixtures, systems with large selectivity are more sensitive to temperature. In addition, this work shows that temperature influences the working capacity of CO2 in temperature swing adsorption (TSA) process with the interplay of pressure, which should be considered in the design of TSA process in practical applications. (C) 2011 Elsevier Ltd. All rights reserved.