In summary, we described disequilibration by sensitization under confinement (DESC) -a process which, in contrast to traditional azobenzene photosensitization systems, utilizes low-intensity visible light energy to shift the E⇄Z equilibrium towards the metastable Z state. The process is based on a coordination cage with two binding sites, which can be filled by two identical molecules of an E-azoarene, a pair of planar dyes, or an azoarene-dye heterodimer. In the latter scenario, the E-azoarene is brought in close proximity to the dye and can be sensitized with low-energy visible light of wavelength depending on the identity of the co-confined dye "antenna". As the sensitizers, we used commercially available and inexpensive dyes, which the confinement effect turns into potent triplet sensitizers. The sensitization is followed by azobenzene isomerization to the Z isomer, to which the cage has low affinity, expelling it in the presence of additional copies of E. On a conceptual level, our system acts as a lightdriven supramolecular machine that converts light into chemical energy in the form of out-of-equilibrium photostationary states, some of which contain unprecedented levels of the metastable Z isomer (98%) that cannot be obtained by direct photoisomerization with any wavelength of light. DESC is a robust process that works with minute amounts of the caged sensitizers, under ambient conditions (no oxygen exclusion necessary), and for a wide range of aromatic and heterocyclic azoarenes. We envision that in the future, the DESC concept will be extended to other classes of photochromic molecules and, more broadly, will become a powerful tool to control chemical reactivity through a combination of light irradiation and confinement.