The ruthenium complexes of dppz (dipyrido[3,2-a:2',3'-c]phenazine) have found wide interest due to their environment-sensitive luminescence and are used, for example, as spectroscopic probes for DNA. The deactivation process for the excited state of the "light-switch" complex [Ru(phen)(2)dppz](2+) (phen = 1,10-phenanthroline) has been studied in water, glycerol, ethylene glycol, and 1,2- and 1,3-propandiol by using fluorescence spectroscopy and single photon counting. In all solvents anomalous temperature dependence is found (increasing quantum yield and excited-state lifetime with increasing temperature). Model-independent analysis shows that only two emissive species, with solvent- and temperature-invariant emission spectral profiles, are sufficient to account for all the data in the polyol solvents. Van't Hoff plots of the ratio of the two species are linear at higher temperatures in all solvents, indicating rapid thermal equilibration of the two species, except for lower temperatures in the most viscous solvent glycerol. Kinetic modeling of the system with microscopic rate constants with positive Arrhenius activation energies requires a third nonemissive species, which is assigned to an excited state with two hydrogen bonds from the solvent, whereas the first two species are assigned to the mono-hydrogen-bonded and non-hydrogen-bonded excited-state species. This assignment is supported by the observation of a growing luminescence intensity as temperature is increased, but no wavelength shift, of high-purity [Ru(phen)(2)dppz](2+) in water solution.