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Exact analytical solutions of the heat‐diffusion problem encountered in the pulsed photothermal evaluation of layered materials are presented. The analysis relates to the long‐time decay of the front face temperature following the absorption of a surface heat pulse. The configuration of a coating on a substrate is analyzed, and the parameters governing the temperature evolution are identified with a particular emphasis on the thermal contact resistance term. This model provides a new method of measuring the quality of the interface. Previously published data and new experiments with laminated materials and living tissues are analyzed using the proposed analytical solutions.