Postsynthetic modification represents an efficient strategy for the fabrication of tunable metal-organic frameworks (MOFs) and derived high-performance functional materials. Herein, we report the synthesis of a mixed-linker zinc(II)-based double-layered MOF (dlMOF) with dual-emissive luminescence, which was further applied as a host matrix to fabricate highly tunable Ln@dlMOF materials (Ln = Eu, Tb, Eu/Tb). The emission characteristics of these materials can be readily modulated over a wide spectrum, including white light emission, by simply tuning the Eu 3+ /Tb 3+ molar ratio in EuTb@dlMOF. Furthermore, by virtue of the difference in thermal sensitivity between triple-emissive sources, the Eu 3+ /Tb 3+ -codoped thermometer EuTb@dlMOF exhibits real-time successive chromogenic switches from red (room temperature) to white (intermediate temperature) to blue/green (cryogenic temperature) emission in a wide temperature region. The versatile performance and the facile assembly from easily available linkers suggest that postsynthetic lanthanide encapsulation represents an efficient strategy for the future engineering of advanced photoluminescent materials with stimuli-responsive and thermochromic properties. © Copyright 2019 American Chemical Society.