We investigated the excited-state proton transfer (ESPT) reaction for 3-cyano-7-azaindole (3CAI) in aqueous solution and in ice. 3CAI undergoes water-catalyzed ESPT in the aqueous solution, giving normal (355 nm) and proton transfer tautomer (∼472 nm) emission bands. Detailed temperature-dependent studies showed that the values of activation free energy (Δ G‡) were similar between N-H and N-D isotopes. Therefore, water-catalyzed ESPT involves a stepwise mechanism incorporating solvation equilibrium ( Keq) to form a 1:1 (molar ratio) water:3CAI cyclic hydrogen-bonded complex as an intermediate, followed by perhaps proton tunneling reaction. In sharp contrast, 3CAI in ice undergoes entirely different photophysical properties, in which 3CAI self-organizes to form a double-hydrogen-bonded dimers at the grain boundary of the polycrystalline. Upon excitation, the dimer proceeds with a fast excited-state double proton transfer reaction, giving rise to solely a tautomer emission (∼450 nm). The distinct difference in ESPT properties between water and ice makes azaindoles feasible for the investigation of water-ice interface property.