Résumé : Stimuli-responsive metal–organic cages (MOCs) have emerged as highly promising candidates for a wide range of applications, from targeted drug delivery to chemical separation, transport and storage of chemicals, and advanced sensing technologies. However, designing MOCs that intelligently respond to stimuli beyond traditional triggers poses a significant challenge. Here we report a strategy of using the unique reactivity of frustrated Lewis pairs (FLPs) to control guest uptake/release within coordination cages. Two triarylphosphine-faced tetrahedral cages (1 and 2) with different degrees of steric hindrance around phosphorus were prepared. The FLP of 1 or 2 with B(C6F5)3 is capable of specifically activating diethyl azodicarboxylate (DEAD) or H2O, respectively. Such reactions modify the charge density and enclosure degree of the cages, allowing for stimulus-controlled guest uptake/release. A two-cage system was deliberately designed to enable selective entrapment and sequential release of different cargoes based on the two orthogonal stimuli (DEAD and H2O). In particular, the order of the stimulus applied dictates the processes of the two-cage system, offering two pathways where all cargoes are either trapped or loaded in solution.