Lanthanide luminescence materials generally show great superiority in light-emitting materials, gaining increasingly exploration in the design of advanced functional materials. Herein, we prepared a supramolecular assembly via the coordination of a host molecule (1) and dilanthanide metal. Compound 1 possesses a 9,10-diphenylanthracene (ant) core with photosensitivity and terminal terpyridine (tpy), containing two-arm dibenzo-24-crown-8. The assembly could exhibit excellent lanthanide luminescence after undergoing a photoreaction from anthracene unit in 1. Significantly, the luminescence of the assembly could be reversibly switched on and off through a regulable photoreaction upon light irradiation or heating. The multiple functional behavior combined with the ease of assembly reveals that this photo/thermo-controlled lanthanide luminescence supramolecular polymer design method offers a convenient pathway for future engineering of multi-stimuli-responsive materials.