In this work an extensive characterization over XeCl multishot laser irradiation was performed at different energy densities and with different thicknesses of graphitic coating superimposed on P and Al implanted 4H–SiC epitaxial layers. It was noted that at 0.6 J/cm2 the 180 nm coating provides a smooth surface unlike lower thicknesses or uncoated treatments. The μ-Raman investigation showed the crystalline quality as a function of the energy density. Through Medium Angle Annular Dark Field-Scanning Transmission Electron Microscopy (MAADF-STEM) and High Angle Annular Dark Field (HAADF)-STEM investigations, the absence of extended defects and the presence of regions with higher density of carbon interstitials (Ci) was revealed. Circular Transfer Length Method (CTLM) measurements demonstrated how irradiation at 0.9 J/cm2 succeeded to reach values of (7.28 ± 1.15) × 102 Ω/sq, lower than the …