The combined effect of the use of carbon fiber and seawater and the molecular structure on the tribological behavior of various polymer materials under natural seawater lubrication was investigated. After the investigation, the wear morphology of the contact surface was observed by a laser scanning confocal microscope, and the texture of the wear scars and tracks were presented in 3D profiles. Moreover, the mechanism of mixed lubrication and wear resistance was analyzed. The results demonstrated that the friction coefficient of carbon fiber-reinforced polyetheretherketone (CFRPEEK) is the lowest and fluctuates at approximately 0.11. Moreover, the seven polymer materials in ascending order of friction coefficients are CFRPEEK, carbon fiber-reinforced polyamide-imide, polytetrafluoroethylene, polyoxymethylene, polyetheretherketone (PEEK), acrylonitrile butadiene styrene resin, and glass fiber–epoxy resin. More critically, the simultaneous incorporation of deposition, polymeric scrap, hydrophilic groups, and seawater resulted in a decrease in the friction and wear of polymer materials under seawater lubrication. This observation implies that a synergistic friction-reducing and wear-resistant effect exists between carbon fiber, seawater, and the molecular structure of PEEK. As a result, a highly effective polymer material was discovered, CFRPEEK, which has the lowest friction coefficient of 0.11 and lowest wear rate of 2 × 10 –5 mm 3·(N·m) −1 among the polymer materials; this validates the selection of dual friction pairs for seawater hydraulic components.