Four kinds of pi-complexation adsorbents are synthesized via ion exchange method or incipient wetness impregnation method with Amberlyst 35, SBA-15, TUD-1, and KIT-6 as supports, and AgNO3 as active ingredient. The samples are characterized by N-2 adsorption/desorption. Fourier transformed infrared spectroscopies, transmission electron microscopy, X-ray diffraction spectrum analysis, and coupled plasma optical emission spectrometry are also used as adsorbents for ethylene/ethane adsorptive separation. The results show that the specific surface area and the dispersion of silver ions affect the separation performance of the adsorbent. Ag-Arnberlyst 35 has the highest ethylene/ethane selectivity among these adorbents while the adsorbed amounts of ethylene of the three mesoporous silica complexation adsorbents are higher. Adsorption thermodynamics analysis suggests that the interaction of ethylene with adsorbent is a mild chemical adsorption. An adsorption kinetics study indicates that the adsorption of ethylene on silver-supported mesoporous materials is not a simple diffusion-control process. The adsorption behavior of ethylene on the pi-complexation adsorbent has an energy barrier in the range of 24-33 kJ/mol. Among the adsorbents in this work, the KIT-6-based adsorbent has the best mass kinetic performance due to its three-dimensional regular interconnected mesoporous structure.