In order to determine the composition of very thin homogeneous layers of multi‐component systems, a reinterpretation of G. A. Hutchins' Method for elemental metal films was worked out. This made it theoritically possible to calibrate for the composition of complex n‐component fims by using massive standards of pure constituents as is done in the case of bulk samples. The method was supplied to very thin layers of AlNi alloys and the results are compared with those obtained by means of emission X‐ray spectrometry.