Lanthanide supramolecular assemblies as photoswitches have attracted much attention in the fields of cellular imaging and light-emitting materials. However, the regulation of lanthanide luminescence behavior by redox of metal ions is rare. Herein, we constructed a lanthanide luminescence supramolecular switch, that is, a binary assembly constructed by mono-(6-ethylenediamine-6-deoxy)-β-cyclodextrin (ECD) and ammonium molybdate tetrahydrate ((NH4)6Mo7O24·4H2O, Mo7), and further assembled into ternary assemblies with polyoxometalate Na9[XW10O36]·32H2O (X-POM, X = Eu and Dy), which was comprehensively characterized by UV-vis, fluorescence, NMR, Fourier transform infrared, dynamic light scattering, scanning electron microscopy, and ζ potential. Thanks to the oxygen-shielding effect of secondary supramolecular assembly, the photoreduction process of Mo7 (VI) could occur rapidly and efficiently. Due to the high Förster resonance energy transfer (FRET) efficiency of X-POM and Mo7 (V) in supramolecular assembly, the photoreduction process is accompanied by fluorescence quenching. In addition, the oxidation process of the Mo7 (V) could be rapidly promoted by heating, which allowed the X-POM fluorescence to recover. Interestingly, ECD-mediated ternary supramolecular assemblies not only tune the lanthanide luminescence but also strongly increase the lanthanide luminescence behavior, leading to the emission of strong narrow red light at 5D0-7F4, which can be successfully applied to two-dimensional code anticounterfeiting. In this study, a new approach is provided for the construction of lanthanide luminescence supramolecular switches tuned by photoreactive polyoxometalate.