Increasing demand for futuristic switches and sensors around the world has created an intense interest in smart materials, which can show a rapid but feature-dependent change in the physical properties in the presence of external stimuli. Hitherto such changes in the photophysical property of materials, specifically in the solid state, are projected for the use of smart on-off switches. Materials having an external-stimuli-responsive change in the photophysical properties like excited-state intramolecular proton transfer (ESIPT) can also be utilized for these purposes. Although the event of solid-state ESIPT is not new in the domain of material chemistry, especially for organic molecules, it was never observed for coordination polymers (CPs). Previous instances of ESIPT in CPs have necessitated the presence of a solvent as a suspension medium, driving a solvent-assisted ESIPT phenomenon. However, the emergence of a solvent-independent ESIPT-enabled CP presents unique advantages. The well-defined periodic arrangement ensures reliable property variations, while the robust coordination bonds between the metal nodes and ligands provide durability in harsh environments. Addressing this gap, we present the first ever solid-state, solvent-free, and solvent-independent ESIPT-active CP. Remarkably, this CP exhibits temperature-dependent ESIPT on-off behavior, demonstrating its potential as a cutting-edge material in the field of smart switches and sensors.