A laser ultrasonics approach to remotely characterize the elastic and thermal properties of a coating-substrate structure, used to protect fuel claddings in lead-bismuth eutectic cooled nuclear reactors, is presented and validated with experimental results. A transient grating geometry is used for multiple wavelength excitation of thermoelastic displacements, and laser beam deflection for detection. The value of Young’s modulus of the coating layer as calculated from the coating’s Rayleigh velocity of 190 ± 50 GPa is in accordance with a nano-indentation measurement. Using a priori knowledge concerning the density and elastic parameters of the coating and substrate, scanning the sample allows the obtaining of a coating thickness map in a fully remote, all-optical way, with an accuracy of about 4 microns for a coating of around 20-micron average thickness. Analyzing the transient thermal grating decay yields a thermal diffusivity value of ( 5.0 ± 1.6 ) × 10 − 6 m 2 /s, in the range of low-carbon steels. The consistency of the results infers that the all-optical laser ultrasonics approach should be feasible for remote inspection of the quality of optically rough coated claddings in the harsh environment of a nuclear reactor.