In this Letter, the effect of a sulfurization treatment carried out at 800 °C on silicon carbide (4H-SiC) surface was studied by detailed chemical, morphological, and electrical analyses. In particular, x-ray photoelectron spectroscopy confirmed sulfur (S) incorporation in the 4H-SiC surface at 800 °C, while atomic force microscopy showed that 4H-SiC surface topography is not affected by this process. Notably, an increase in the 4H-SiC electron affinity was revealed by Kelvin Probe Force Microscopy in the sulfurized sample with respect to the untreated surface. The electrical characterization of Ni/4H-SiC Schottky contacts fabricated on sulfurized 4H-SiC surfaces revealed a significant reduction (∼0.3 eV) and a narrower distribution of the average Schottky barrier height with respect to the reference untreated sample. This effect was explained in terms of a Fermi level pinning effect induced by surface S incorporation.