An extensive photophysical characterization of 3-chloro-4-methylumbelliferone (3Cl4MU) in the ground-state, S(0), first excited singlet state, S(1), and lowest triplet state, T(1), was undertaken in Water, neutral ethanol, acidified ethanol, and basified ethanol. Quantitative measurements of quantum yields (fluorescence, phosphorescence, intersystem crossing, internal conversion, and singlet oxygen formation) together with lifetimes were obtained at room and low temperature in water, dioxane/water mixtures, and alcohols. The different transient species were assigned and a general kinetic scheme is presented, summarizing the excited-state multiequilibria of 3Cl4MU. In water, the equilibrium is restricted to neutral (N*) and anionic (A*) species, both in the ground (pK(a) = 7.2) and first excited singlet states (pK(a)* = 0.5). In dioxane/water mixtures (pH ca. 6), substantial changes of the kinetics of the S(1) state were observed with the appearance of an additional tautomeric T* species. In low water content mixtures (mixture 9:1 v:v), only the neutral (N*) and tautomeric (T*) forms of 3Cl4MU are observed, whereas at higher water content mixtures (water mole fraction superior to 0.45), all three species N*, T*, and A* coexist in the excited state. In the triplet state, in the nonprotic and nonpolar solvent dioxane, the observed transient signals were assigned as the triplet-triplet transition of the neutral form, N*(T1) -> N*(Tn). In water, two transient species were observed and are assigned as the triplets of the neutral N*(T1) and the anionic form, A*(T1) (also obtained in basified ethanol). The phosphorescence spectra and decays of 3Cl4MU, in neutral, acidified, and basified solutions, demonstrate that only these two species N*(T1) and A*(T1) exist in the lowest lying triplet state, T(1). The radiative channel was found dominant for the deactivation of the anionic species, whereas with the neutral the S(1) (sic) S(0) internal conversion competes with fluorescence. For both N* and A* the intersystem crossing yield represents a minor deactivation channel for S(1).