Dual-interface energy transfer multilayer nanoparticles hold great promise for X-ray photonic applications such as tumor therapy, information encryption, and high-resolution imaging due to their tunable multi-modal luminescence. However, current systems remain limited in interfacial structure construction, energy transfer efficiency, and energy regulation under multi-wavelength excitation. Here, we employ dual-interface energy transfer (IET) engineering to precisely construct a core–shell–shell architecture via ion layering and doping control, achieving dual-mode response to X-rays and 254 nm ultraviolet (UV) light. This strategy significantly enhances luminescence performance and demonstrates strong potential in multi-modal display, information encryption, and imaging, providing a new material platform for advanced photonic devices.