Abstract: Sampling by laser ablation in hyphenation with ICP-AES was applied to the analysis of coating of metal materials, and 6 typical samples were taken for the analysis. Data of components or elements in the coating layer and in the matrix, as well as the thickness of the coating were found. At the same time, some other conditions for ablation, i.e. energy level of laser, pulse frequency, bore diameter of ablation and flow-rate of carrier gas were also optimized. A timing-resolution graph was obtained by plotting values of signal intensity vs. time of ablation from which the line of demarcation between coating and matrix was determined from the data of variation of signal intensities of elements of coating and of matrix collected in definite time interval; and on the base of sustained time for the appearance of signal of element of the coating, thickness of coating layer was calculated by a given formula. It was found that values of thickness of coatings of the 6 samples were found to check quite well with the values obtained by the method of metallography.