The paper investigated the deposition sequence-dependent behavior of Ni (50 nm)/Ti (60 nm)/W (60 nm) and Ni (50 nm)/W (60 nm)/Ti (60 nm) Ohmic contacts on n-type 4H-SiC after annealing at 1050 °C for 3 min in Ar atmosphere by in-depth electrical and physical characterization. The contact resistivity of the Ni/Ti/W structure (∼ 8.43 × 10−6 Ω·cm2) was found to be lower than that of the Ni/W/Ti structure (∼ 21.9 × 10−6 Ω·cm2). For the Ni/W/Ti structure, the W layer closer to the contact interface led to an increase in the preferred orientation degree of the δ-Ni2Si (220) plane at the interface, favoring a lower contact resistivity according to previous studies. However, the content and interfacial coverage of δ-Ni2Si is reduced by the WxNiyC phase and the interfacial strain/stress is greatly increased by the WxNiyC phase as well, which ultimately leads to an increase in the contact resistivity. The larger interfacial strain/stress in the Ni/W/Ti structure also results in a rough surface morphology with more microcracks and a large area of delamination. In addition, the shearing strength of Al wire bonding points on the Ni/W/Ti surface is slightly weaker than that on the Ni/Ti/W surface due to the higher surface roughness. The above experimental findings can provide a guideline for further structural optimization of the 4H-SiC Ohmic contacts.