Tribological properties of MoS2/C coatings with different carbon contents (44.7–84.3 at.%) deposited by magnetron sputtering were systematically investigated under atmospheric environment. During tribological tests, the coating with the least MoS2 content exhibited the lowest friction coefficient and wear rate, while coating with the most MoS2 showed the worst performance. To understand friction and wear mechanism, multiple analytical tools such as SEM, EDS, Raman, XPS and TEM were applied to investigate the composition and structure. TEM and SEM characteristics proved that the tribofilm with multilayered structure was formed on the tribopair. The C-rich layer adhered to the tribopair and the top layer was well-ordered MoS2 tribofilm, and the dominated amorphous MoS2 was found between the two layers. It suggested that the shear plane was mainly made of well-ordered MoS2 transfer film, while carbon improved the mechanical properties of the coatings, served as a lubricant and also inhibited the oxidation of MoS2.