The thermostability of encapsulated xenon is investigated in a series of isostructural crystalline sorbents. These sorbents consist of metal-organic capsules, with the general formula of [ConFe4-nL6]4- (n = 1, 2, 3 and 4), where L2- is an organic linker with two sulfonate groups. In the crystalline sorbent, guanidinium cations form H-bond networks with the peripheral sulfonate groups in the solid state and trap xenon in the molecular cavities, which are at least 2.7 times the volume of xenon. When heated, the sorbent retains xenon up to 561 K, i.e., 396 K higher than the boiling point of xenon. Furthermore, the thermostability of trapped xenon can be modulated by varying the ratio of Co:Fe in the crystalline sorbent. Elemental analysis on a single crystal by energy dispersive X-ray spectroscopy confirms the homogeneous distribution of Co and Fe in the sorbent. Structural analyses reveal that the expansion of capsule cavity is proportional to the Co:Fe ratio, with increases of 0.049(1) Å and 6.4(8) Å3 in metal-metal distance and cavity volume, per substitution of Fe by Co center. Steric repulsion between peripheral sulfonate groups is found to render a hypothetical face-centered cubic structure of (C(NH2)3)4[Fe4L6] not accessible, which would have trapped xenon with exceptional thermostability. The stable and tunable trapping of xenon in crystalline sorbents by over-sized molecular cavities suggests a new strategy for separation and storage of xenon, through introduction of kinetic barriers, such as H-bond networks.