Polyphenylene sulfide (PPS) based composites were prepared by hybridization between multiscale carbon fiber (CF) and polytetrafluoroethylene (PTFE) fiber, with, meanwhile, PPS serving as matrix, to obtain the interlocking network structure of CF-PTFE fiber hybridization. Dynamic rheological behavior distinctly illuminates the formation of the effective network structure situated inside the composites, which can effectively improve the tribological properties of the composites. Additionally, the PPS/PTFE/short carbon fiber (SCF) composites possess better friction and wear properties, compared with PPS/PTFE/micrometer carbon fiber (MCF) composites. More importantly, the PPS/PTFE/SCF20 composites are endowed with the lowest friction coefficient of about mu = 0.103, under the dry-sliding condition. Studying the transfer film and worn surface of composites, the results demonstrated that the wear mechanism gives priority to adhesive wear and accompanying abrasive wear; furthermore, tribochemical reaction occurs in the sliding process by energy dispersive X-ray spectroscopic (EDS) and X-ray photoelectron spectrscopic (XPS) analysis. The study of self-lubricating composites of multiscale CF-PTFE fiber hybridization has important application prospects in mechanical devices for the military, aerospace industry, and automotive industry.