Abstract: | Herein, we report an approach to combat counterfeiting and storage of valuable information based on the solid‐state fluorescence switching behavior of isoniazid functionalized naphthalene diimide (ISO_NDI) in response to an external stimuli (i. e., HCl vapor). The unique feature of ISO_NDI is further utilized to develop an invisible ink (ISO_NDI‐PVA) with commercial polymer polyvinyl alcohol (PVA). A solid‐state fluorescence recovery was observed while loading with HCl vapors. This exclusive property of the material could be applied directly as a security ink for confidential data storage purpose. Based on above strategy, we successfully realized the rewritable application by using ISO_NDI‐PVA ink and confirm its practical efficacy on various substrates by creating different patterns. The solid‐state fluorescence switching behavior of ISO_NDI‐PVA ink exhibited reversible on/off signal for multiple cycles under the influence of HCl/NH3 vapors. Mechanistic investigation supports a clear participation of intermolecular charge transfer (ICT) phenomenon in the solid‐state fluorescence switching property. The ease of fabricating the ink with invisible to visible characteristics in response to HCl vapors provides new opportunities for exploring the application of ISO_NDI‐PVA as invisible ink for targeted security applications. |