The fluorescence of 7-hydroxy-4-methylcoumarin and 4-carboxymethyl-7-hydroxycoumarin and some simple derivatives, has been examined. For compounds having a free 7-hydroxy-group, complex fluorescence spectra were obtained when solvents containing water were employed. The complexity is in part due to the ground state equilibrium, phenol ⇄ phenolate anion. This means that unless the excitation wavelength is carefully selected, more than one species is excited. Four fluorescent species, derived from the phenol, were observed in various aqueous alcohol systems: two species were identified as the excited phenol and its anion and the other two tentatively identified as an intimate and sovent separated ion-pair. From steady state, fluorescence measurements and time resolved ns fluorescence spectroscopy the inter-relation of these various excited states was established. The role of water in these systems is discussed.