Fiber hybrid polyimide-based (PI-based) composites reinforced with carbon fiber (CF) and poly-p-phenylene benzobisthiazole (PBO) fiber of different volume fractions were fabricated by means of hot press molding technique, and their mechanical properties and tribological behaviors under sea water lubrication were systematically investigated in relation to the synergism of CF and PBO fiber. Results showed that the incorporation of CF or PBO fiber improved the tensile strength, hardness, and wear resistance of PI. More importantly, because of the synergistic enhancement effect between CF and PBO fiber on PI matrix, the combination of 10%CF and 5%PBO fiber reinforced PI-based composite had the best mechanical and tribological properties, showing promising application in ocean environment.