The application of time-resolved laser induced fluorescence spectroscopy (TRLIF) to the complexation studies of Eu(III) and Cm(III) with humic substances is described. Using this method, three different spectroscopic characteristics(excitation spectra, emission spectra, and lifetimes) of these aquo ions and their complexes can be directly measured. By observing shifts in the wavelength and changes in the lifetime and intensities of the fluorescence emission, the information on the complexation behavior of humic substances with these trivalent metal cations in an aqueous solution, as well as energy transfer mechanisms, can be obtained. In addition, this method allows precise spectroscopic quantification of the complexation processes at very low concentrations of both components.