Joints of high thermal contact conductance and electrical insulation have been obtained by coating copper supports with thin alumina (Al2O3) layers (of 140–150 μm thickness). This has been achieved by a combination of plasma spraying process and the subsequent coating remelting by a near-Infrared (n-IR) laser. With a proper optimization of the laser processing conditions, it is possible to transform the metastable γ-Al2O3 phase of the as-sprayed coatings to stable α-Al2O3, and to achieve denser alumina coatings. This results in a large enhancement of the thermal conductance of the joints, enabling their application as heat sinks at cryogenic and ambient temperatures. The process proposed in this work is scalable for the formation of alumina coatings on large metallic pieces of complex geometries.