WS2/a‐C multilayer films exhibit good friction reduction but relatively low hardness and load‐bearing capacity. To further enhance the tribological properties of WS2/a‐C films, Mo layers with different thicknesses are introduced into WSx/a‐C multilayer films to fabricate WSx/Mo/a‐C/Mo multilayer films by magnetron sputtering. The microstructure and tribological properties of the films are characterized by X‐ray diffractometry, scanning electron microscopy, nanoindentation, and ball‐on‐disk tribotesting. The results show that the WSx/Mo/a‐C/Mo multilayer films have better mechanical and tribological properties than WSx/a‐C multilayer films. With increasing Mo single‐layer thickness, the hardness of the multilayer films initially increases and then decreases slightly; moreover, an increased elastic modulus and decreased adhesion are observed. The multilayer film with an Mo single‐layer thickness of 2 nm demonstrates the optimal set of comprehensive properties (i.e., a maximum hardness (H)/elastic modulus (E) ratio of 0.0793, H3/E2 ratio of 0.0812 GPa, binding force of 30.4 N, minimum friction coefficient of 0.187, and wear rate of 1.01 × 10−14 m3 N−1 m−1).