Noble gas (Ng) elements are stable because of their octet electronic configuration, and thus Ng capture and purification are highly challenging. Here, we show a new concept for these applications: an orbital trap for Xe. This concept was found in Xe adsorption/separation processes at room temperature (RT) at the single Ag­(I) site in MFI zeolite. Experiments and calculations showed the zeolite lattice-coordinated Ag­(I) single ion has excellent electron-accepting nature and thereby induces the Xe 5p → Ag­(I) 5s donation orbital interaction, forming a stable σ-bond with Xe even in the lower-pressure region and at RT. By contrast, the stable σ-bond for Kr adsorption is not established at RT because of the instability of the orbital interactions of the Kr 4p → Ag­(I) 5s donation, as reflected from the relatively high energy of the Kr 4p orbital. Thus, the single Ag­(I) site allows it to distinguish between Xe and Kr at RT; the Xe separation from the Xe/Kr gas mixture was achieved at RT using the Ag/MFI containing a high concentration of single Ag­(I) sites. Our findings suggest that the orbital Xe trap using the local structure of porous materials shows promise as an efficient approach to selectively collect Xe (air concentration 0.087 ppm only). It will help to expand the range of applications of the costly Xe.