In this work, we investigated the electrical properties evolution of Mo/4H-SiC Schottky contacts following thermal annealing treatments at temperature up to 950 °C. The electrical characterization under forward and reverse bias revealed a reduction of the barrier height from 1.45 eV (as-deposited contact) to 1.30 eV (950°C-annealed contact), with the presence of inhomogeneity in the contact, while the leakage current followed a thermionic-field emission (TFE) model after annealing at 750 °C and presented a significant increase for the 950°C-annealed contact. The electrical characterization was associated with microstructural analyses, which highlighted an enlargement of the grains forming the structure of the Mo-film and the presence of voids near the Mo/4H-SiC interface. These observations can be at the base of the variation in the electrical behavior of the contact.