The Ni contact layer was deposited on semi-insulating 4H-SiC substrate by magnetron sputtering. The as-deposited samples were treated by rapid thermal annealing (RTA) and KrF excimer laser thermal annealing (LTA), respectively. The RTA annealed sample is rectifying while the LTA sample is Ohmic. The specific contact resistance (ρc) is 1.97 × 10−3 Ω·cm2, which was determined by the circular transmission line model. High resolution transmission electron microscopy morphologies and selected area electron diffraction patterns demonstrate that the 3C-SiC transition zone is formed in the near-interface region of the SiC after the as-deposited sample is treated by LTA, which is responsible for the Ohmic contact formation in the semi-insulating 4H-SiC.