1H,1H,2H,2H-Perfluorooctyl trichlorosilane (PFTS) was used to modify TiO₂ nanoparticles, and hydrophobic PFTS–TiO₂ nanoparticles were obtained by an ultrasonic reaction method. The PFTS–TiO₂ surface morphological and hydrophobic properties were analyzed with scanning electron microscopy (SEM), Fourier transform infrared spectrometry, and contact angle (CA) testing. Then, the poly(p-phenylene benzobisoxazole) fabric–phenolic composite filled with PFTS–TiO₂ as a lubricant additive was fabricated by a dip-coating process. The tribological properties of the composite were investigated, and the wear surface morphology was observed by SEM. The experimental results show that the water CA of the composite filled with PFTS–TiO₂ was 158°, and the composite containing 4 wt % PFTS–TiO₂ exhibited excellent antifriction and abrasion resistance. The hydrophobic surface of the composite showed excellent durable performance with a static water CA of 126.7° after abrasion.