Magnesium alloys are the lowest-density structural metals with a wide range of applications, such as aircraft skins, engine casings and automobile hubs. However, its low surface hardness and non-corrosion resistance in natural environments limit its wide range of applications. In this work, Si-DLC coatings (Si: 15 at.%) are fabricated on AZ91 alloy using a hollow cathode discharge combined with a DC bias voltage from 0 to −300 V to increase the deposition rate and modulate the structure and properties of the coatings. The Si interlayer with a thickness of around 0.6 µm is deposited first to enhance the adhesion. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy are used to investigate the effect of DC bias on the microstructure evolution of Si-DLC coatings. Meanwhile, corrosion and wear resistance of the coatings at various bias voltages have been investigated using electrochemical workstations and pin-on-desk wear testers. It is shown that the bias-free coating has a loose structure and is less resistant to corrosion and wear. The bias coating has a compact structure, small carbon cluster size, high chloride ion corrosion resistance, and high wear resistance against Al₂O₃ spheres. The corrosion potential of the coating bias at −300 V is −0.98 V, the corrosion current density is 1.35 × 10⁻⁶ A·cm⁻², the friction coefficient is 0.08, and the wear rate is 10⁻⁸ orders of magnitude. The formation of SiC nanocrystals and high sp³-C, as well as the formation of transfer films on the surface of their counterparts, are the main reasons for the ultra-high wear resistance of the bias coatings. The wear rate, coefficient of friction, and corrosion rate of the coating are 0.0069 times, 0.2 times, and 0.0088 times that of the AZ91 alloy, respectively. However, the bias coating has only short to medium-term protection against the magnesium alloy and no long-term protection due to cracks caused by its high internal stress.