To reduce wear and energy loss during the movement of miniaturized devices such as wearable devices and MEMS, and to address the inherent limitations of individual categories of solid lubricating materials, a new MXene-based composite solid lubricating material was designed. In this study, Ti3C2Tx@MoS2 composites were successfully prepared via hydrothermal synthesis, with MoS2 nanosheets grown uniformly on the surface and interval of the multilayer Ti3C2Tx. The composites were deposited as a solid lubricant coating on silicon substrates using a drop coating method. Tribological behavior was evaluated by ball-on-disk reciprocating and rotating tribometer, respectively. The results revealed that the friction coefficients of the multilayer Ti3C2Tx@MoS2 composite coatings were reduced by 75%, 69%, and 58%, respectively, compared to the multilayer Ti3C2Tx, MoS2, and their mechanical mixtures. Moreover, this study proposed the excellent wear resistance of the multilayer Ti3C2Tx@MoS2 composite coatings was attributed to the synergistic lubrication of Ti3C2Tx and MoS2. MoS2 was enriched in the wear track, and the tribofilm formed during friction process played the role of friction reduction and lubrication. In comparison, the multilayer Ti3C2Tx had an excellent effect on the wear resistance and structural support.