This study investigated the impact of deposition pressure on the microstructure and tribological properties of B/WS2 composite coatings deposited via unbalanced magnetron sputtering. Deposition pressures of 0.6 Pa, 0.8 Pa, 1.0 Pa, 1.2 Pa, and 1.4 Pa were used during the deposition process. The microstructure and mechanical properties of the B/WS2 composite coatings were characterized, and friction and wear experiments were conducted. The study found that the microhardness of the B/WS2 composite coatings decreased as the deposition pressure increased. The highest hardness of the coating, reaching 8.1GPa, was observed at a deposition pressure of 0.6 Pa. This was due to the formation of Tungsten tetraborate (WB4) during the deposition process, which had a high hardness and improved the mechanical properties of the coating. The wear life of the B/WS2 composite coatings was at its best, reaching 9.9 × 104 cycles, and the friction coefficient was at its lowest when the deposition pressure was 1.2 Pa. Selecting an appropriate deposition pressure can improve the tribological properties of B/WS2 composite coatings. Doping Boron can improve the hardness and wear resistance of the composite coatings. Abrasive wear and spalling are the two main wear forms of B/WS2 composite coatings.