Protective coatings are the first line of defense of vessels against the corrosive marine environment. For this reason, painting process and maintenance tasks derived are critical in the protection of the metallic structure of a ship. In particular, an adequate film thickness is necessary for a coating system to fulfil the requirements and provide good anti-corrosion protection. In this sense, both under thickness and over application can cause failures.In this work, laser-induced plasma spectroscopy (LIPS) is proposed for the characterization of the composition and thickness of the protective coatings used in the naval sector, in order to overcome some of the limitations of thickness gauges using ultrasound, commonly used. Compositional characterization together with thickness measurements of painting layers has simultaneously been obtained by LIPS and tested for quality control purposes.The results demonstrate the potential of this technique to perform the on-line chemical and thickness characterization of applied painting layers in order to improve the control of the process and to avoid coating defects.