Depth profile analysis by means of laser induced breakdown spectroscopy (LIBS) was investigated with respect to its potential to measure the thickness of different types of thin calcium phosphate used as biomimetic coatings on Ti6Al4V alloy. The coating thickness is determined from the ratio of the intensities of a calcium line and a titanium line measured at burst energy high enough to penetrate the coating with a single burst. To achieve an ablation depth in the range of the coating thickness of about 10 μm a Nd: YAG laser at 532 nm in single shot mode was used. The achieved thickness resolution is estimated to about 500 nm for coating thicknesses of electrolytically deposited calcium phosphate in the range of 1.0 to 10.0 μm.