In this work we studied different Schottky contacts to 4H-SiC with the aim to obtain Schottky Barrier diodes (SBDs) and Junction Barrier Schottky diodes (JBS) able to operate at high temperatures, frequencies and power densities with low power losses. Schottky contacts were fabricated using Mo and Mo/Al layers annealed up to 600 °C using a Rapid Thermal Process (RTP). A comparison with previous results obtained with Ni, Ti and Ti/Al layers annealed up to 400 °C is also proposed. The Schottky contacts were characterized by means of standard Current-Voltage (I-V) and Capacitance-Voltage (C-V) techniques. X-ray Photoelectron Spectroscopy (XPS) analyses were performed in depth profile mode in order to study the structural evolution of the interface Mo/SiC and Al/Mo during annealing treatments. Mo/Al contacts show a lower barrier height and better overall performances in forward polarization when compared to the Ti- and Ni-based contacts, and they are very promising for Schottky contact fabrication on SBD and JBS.