ESIPT‐Active Pyrene‐imidazole Fluorophores: GSIPT, Dual Solid‐ and Solution‐State Emission plus Counter‐Intuitive Crystal Packing**

Abstract We report a new excited‐state intramolecular proton transfer (ESIPT)‐inspired hydroxyl (OH)‐substituted pyrene‐imidazole that promote unprecedented intramolecular proton transfer in the ground state (GSIPT). The enol and keto isomers are in equilibrium, with a high keto‐isomer component in the solid state. In conjunction with DFT calculations, the photophysical studies and crystal structure analysis shred substantial evidence for the ground state transformation. The ESIPT‐active compounds also show the rare feature of high dual solution (φ f =70 %) and solid state (φ f =41 %) emission characteristics and counter‐intuitive stronger intermolecular interactions in the solid state versus the ESIPT‐inactive counterparts.