In this study, galvanic coatings of Cu and Ni, typically applied in industrial standard routines, were investigated. Ablation experiments were carried out using the first two harmonic wavelengths of a pulsed Nd:YAG laser and the resulting plasma spectra were analysed using a linear Pearson correlation method. For both wavelengths the absorption/ablation behaviour as well as laser-induced breakdown spectroscopy (LIBS) depth profiles were studied varying laser fluences between 4.3–17.2 J/cm2 at 532 nm and 2.9–11.7 J/cm2 at 1064 nm. The LIBS-stratigrams were compared with energy-dispersive X-ray spectroscopy of cross-sections. The ablation rates were calculated and compared to theoretical values originating from a thermal ablation model. Generally, higher ablation rates were obtained with 532 nm light for both materials. The light–plasma interaction is suggested as possible cause of the lower ablation rates in the infrared regime. Neither clear evidence of the pure thermal ablation, nor correlation with optical properties of investigated materials was obtained.