With the help of an α-ray-L-x-ray coincidence setup, elemental and isotopical concentrations of alpha-emitting isotopes can be measured. This method seems to be appropriate for analyzing complex alpha spectra. The anticipated coincidence counting rate is derived from atomic and nuclear properties for different actinides isotopes. It ranges from 1 to 107 s-1 per isotope and gram of spent reactor fuel (40 GWd/t, with a 3-yr cooling time). For the heavier actinides, this rate surpasses the random coincidence counting rate (∼1 × 103 s-1), thus the feasibility of the method can be expected. Uranium and plutonium, however, are not detectable in the presence of the heavier actinides.