A sandwich structure of Ni/V/4H-SiC was prepared and annealed at different temperatures from 650 °C to 1050 °C. The electrical properties and microstructures were characterized by transmission line method, X-ray diffraction, Raman spectroscopy and transmission electron microscopy. A low specific contact resistance of 3.3 × 10-5 Ω·cm2 was obtained when the Ni/V contact was annealed at 1050 °C for 2 min. It was found that the silicide changed from Ni3Si to Ni2Si with increasing annealing temperature, while the vanadium compounds appeared at 950 °C and their concentration increased at higher annealing temperature. A schematic diagram was proposed to explain the ohmic contact mechanism of Ni/V/4H-SiC structure.