DC magnetron sputtering was used to depositmolybdenumboridethin films for potential low-friction applications. The films exhibit a nanocomposite structure with ∼10 nm large MoB2−x (x > 0.4) grains surrounded by a boron-rich tissue phase. The preferred formation of the metastable and substoichiometric hP3-MoB2structure (AlB2-type) is explained with kinetic constraints to form the thermodynamically stable hR18-MoB2 phase with a very complex crystal structure. Nanoindentation revealed a relatively high hardness of (29 ± 2) GPa, which is higher than bulk samples. The high hardness can be explained by a hardening effect associated with the nanocomposite microstructure where the surrounding tissue phase restricts dislocation movement. A tribological study confirmed a significant formation of a tribofilm consisting of molybdenum oxide and boron oxide, however, without any lubricating effects at room temperature.