Humid air is a very important service environment, in which metal friction parts should be enhanced to offer excellent corrosion resistance and wear resistance. The B4C coating is an excellent candidate material to enhance the corrosion resistance and tribological behaviors. The purpose is to investigate the effect of negative bias voltages on the tribological properties of B4C coatings under a high relative humidity environment. Amorphous B4C coatings were successfully prepared by closed field unbalanced magnetron sputtering technology and its microstructure, hardness, elastic modulus, adhesive force and tribological properties were systematically studied. Results demonstrate that the B4C coatings deposited at each negative bias voltage have a columnar structure and the surface roughness remained unchanged (about 1.0 nm), while the thickness, hardness, elastic modulus and adhesion force increase first and then decrease with the negative bias voltage increasing. Among them, the B4C (-50 V) coating showed the best mechanical properties. It should be noted that the B4C (-50 V) coating with an excellent corrosion resistance also exhibits the lowest friction coefficient (similar to 0.15) and wear resistance (7.2 x 10(-7) mm(3)center dot N-1 center dot m(-1)) under humid air (85% RH). This is mainly due to the tribochemical reaction of B4C during a sliding process to produce boric acid at the sliding interface. B4C coatings can provide an excellent corrosion resistance and high wear resistance due to their high chemical stability and high hardness.