Two new coordination compounds of rare earth chloride with N-acetyl-DL-alanine and imidazole have been prepared from absolute alcohol. The general formula RE(C5H8NO3)2(C3H5N2)2Cl3·4H2O (RE=Ce, Pr) of these compounds were identified, by chemical and elemental analysis, FTIR spectra, UV spectra, 1H NMR and 13C NMR spectra, and molar conductance. The processes of thermal decomposition were identified by TG-DSC curves. The possible reaction mechanisms and the kinetics equation were investigated by comparing the kinetics parameters. The activation entropy of dehydration, as well as enthalpy values of dehydration and decomposition were obtained by DSC curve. The three-dimensional fluorescence spectra of liquid compounds were measured. The phenomenon of the up-conversion fluorescence is discussed.