The electronic transition maxima of three solvatochromic probes were measured at temperatures between (-13.5 and 70 degreesC) in five liquid hydrofluoroether (HFE) solvents. The electronic transition maxima were used to calculate thermosolvatochromic Kamlet-Taft parameters. The solubilities of naphthalene and benzoic acid were measured in the HFE solvents, and a linear solvation energy relationship (LSER) was calculated to model the solubility data using the measured Kamlet-Taft thermosolvatochromic parameters. Differences between the Kamlet-Taft values of the pure hydrofluoroethers and azeotropic mixtures of the hydrofluoroethers are discussed, along with the LSER results.