2-(2'-Hydroxyphenyl)benzoxazole (HBO) substituted at the 5'-position with bipyridylvinylene phenylenevinylene (compound 2) produces both normal and, via an excited-state intramolecular proton transfer (ESIPT) reaction, tautomer emissions in solvents that preserve intramolecular hydrogen bonds. The abundance of the tautomer emission from compound 2 in a poor hydrogen-bonding solvent increases in response to the application of a higher excitation energy. Based on quantum chemical calculations, the excitation-dependent dual emission is consistent with a model in which the ESIPT reaction is more favored in the S2 than in the S1 electronically excited state.