Steady-state and time-resolved fluorescence techniques, in addition to quantum mechanical calculations, were employed to study the excited-state proton transfer (ESPT) to solvent of three 7-hydroxycoumarin dyes. We found that for 7-hydroxycoumarins in water, the ESPT rate is high, about 2 X 10(10) s(-1), whereas in methanol the ESPT rate is much lower than that over the nonradiative lifetime of the excited singlet state; thus, the ESPT efficiency is very low.