Disordered boron carbide coatings with their high hardness, high lubricity, and low surface friction have become the coatings of choice to enhance the wear performance of man!, existing products. These coatings have been successfully commercialized using a magnetron sputtering process. In this paper, the effects of one of the critical process parameters, bias voltage, on the chemistry, microstructure, and the properties of the coatings are discussed. In combination with microstructure examination, special emphasis was made on nanoscopic level chemical analyses in order to explain the effects of this process parameter. The substrate bias was found to have strong effects on the hardness and the stress of the coating, but it has little influence on the frictional characteristics of the coating. The results of the examination and the analyses of the coating using FTIR, XPS, TEM, PEELS, and SIMS revealed that the morphology of the coating changed from a columnar structure to a continuous solid structure as the substrate bias voltage increased from 0 to 200 V. Oxide species were found in between the columns, while the columns mainly consisted of boron carbide with a boron to carbon atomic ratio of about 4. The atomic ratio of boron to carbon appeared to be independent of the substrate bias.