An AlCrSiWN coating was prepared on a cemented carbide substrate by the arc ion plating technology. The optimization of the coating process was carried out by matrix analysis of orthogonal experiments to calculate the influence of the process parameters on the hardness, bonding and roughness indexes of the coating, determine the optimal coating process parameters, and focus on the influence of the bias voltage on the microscopic morphology, mechanical properties and friction properties of the coating. The results showed that the influence of the process parameters on the indexes of the orthogonal experiments was in the following order: bias voltage > arc current > N2 flow rate. The optimal solution was achieved with an arc current of 160 A, a bias voltage of −80 V, and a N2 flow rate of 600 sccm. Properly increasing the bias voltage improved the microscopic morphology, mechanical properties and wear resistance of the coating. When the bias voltage was −80 V, the coating surface presented fewer large particles with a less uniform size and no obvious crater defects; in addition, the cross-sectional structure changed from grape-like to columnar, and the coating had higher hardness, lower roughness and better bond strength. In the friction performance test, coating at a −80 V bias voltage showed better wear resistance, which was reflected in lower friction coefficient and wear, and the wear mechanism mainly consisted of adhesion and oxidation wear.