Laser Induced Breakdown Spectroscopy (LIBS) is a potential candidate to monitor the layer composition and fuel retention during and after plasma shots on specific locations of the main chamber and divertor of ITER. This method is being investigated in a cooperative research programme on plasma devices such as TEXTOR, FTU, MAGNUM-PSI and in other various laboratorial experiments. In this paper LIBS results from targets of D–H-rich carbon films and mixed W–Al–C deposits on bulk tungsten substrates are reported (simulating ITER-like deposits with Al as proxy for Be). Two independent methods, one to determine the relative elemental composition and the other the absolute contents of the target based on the experimental LIBS signals are proposed. The results show that LIBS has the capability to provide the relative concentrations of the elements on the deposited layer when the experimental conditions on the targets surface are identical to the calibration samples.