WB2 nanocomposite coatings were synthesized by dc magnetron sputtering. The morphology, chemical composition, chemical bonding state, microstructure, hardness, and tribological properties were investigated. The columnar‐structured coatings are dense and uniform. The as‐deposited coatings were found to have a metastable AlB2‐type structure as characterized by X‐ray diffraction and further confirmed by high‐resolution transmission electron microscopy. Coatings exhibit superhardness about 43.2 ± 5 GPa (taken from the plateau region) obtained by nanoindentation. In addition, the steady‐state friction coefficient µ = 0.23 and wear rate K = 6.5 × 10−6 mm3 N−1 m−1 were obtained under dry sliding condition in ambient environments. These characteristics indicate AlB2‐type WB2 coatings have high potential application as superhard and low wear coatings. Moreover, the AlB2‐type WB2 can hardly be prepared using the conventional powder metallurgy technology without high pressure, and this study proposes a new practical approach to prepare it.