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1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), which forms weak hydrogen bonds despite the high basicity caused by its hindered structure, was used to investigate tautomer formation via excited-state intermolecular proton-transfer (ESPT) reactions. The kinetics of the ESPT reactions of anthracen-2-yl-3-phenylurea (2PUA) in the presence of DBU were compared to that observed for the acetate anion (Ac) using time-resolved fluorescence measurement. Based on the association constants in the ground state, the intermolecular hydrogen bond between 2PU