LAUSR

Materials exhibiting reversible changes of their photoluminescence properties upon exposure to heat have an immense potential in various advanced photonic applications. Particularly, the control over an on‐demand response of thermochromic luminescent materials (TLMs) similar to a chameleon is of great importance. However, it is still difficult and challenging to achieve it. Therefore, this paper reports a simple and effective way to construct TLMs, which involves the incorporation of the metal–ligand complexes into polyethylene glycol (PEG). Ratiometric or off–on response modes of these TLMs can be tuned by incorporating metal complexes based on either Zn2+ or Co2+ into PEG and by taking advantage of reversible metal–ligand coordination, dissociation, or excited‐state conformation changes of the resulting materials. Moreover, by choosing PEG matrices with different molecular weights, the thermochromic transition temperatures of these TLMs can be tuned. It is also demonstrated that the controllable response behavior of these chameleon‐like TLMs can be used in applications related to real‐life anti‐counterfeiting and security printing. This work opens novel opportunities for the development of smart materials with controllable responses useful for advanced photonic applications.