This review introduced the preparation and structural characterization of polyelectrolyte multilayers in recent years and also summarized the tribology research progress of the polyelectrolyte multilayers, including tribological properties, surface adhesion characteristics, and wear resistance properties. Statistics analysis indicated that nanoparticlesdoped polyelectrolyte multilayers present better friction and wear performance than pristine polyelectrolyte multilayers. Furthermore, the in situ growth method resulted in improved structural order of nanoparticles composite molecular deposition film. In situ nanoparticles not only reduced the molecular deposition film surface adhesion force and friction force but also significantly improved the life of wear resistance. That was due to the nanoparticles that possessed a good load-carrying capacity and reduced the mobility of the polymer-chain segments, which can undergo reversible shear deformation. Based on this, further research direction of in situ nanoparticles molecular deposition film was proposed.