Nano-micro hierarchical porous polyphenylene sulfide/polytetrafluoroethylene (PPS/PTFE) composites were prepared by mold-leaching and vacuum melting process under high temperature condition. The tribological behaviors of porous PPS/PTFE composites and the synergism as a result of incorporation of both micro-porogen (NaCl) and mesoporous TiO2 whiskers were investigated. The effects of mesoporous TiO2 whiskers and nonperforated TiO2 whiskers on the friction and wear properties of PPS/PTFE composites were comparatively studied, respectively. Results indicated that the wear rate of porous PPS/PTFE composites with 30 wt % NaCl and 7 wt % mesoporous TiO2 whiskers obtained the lowest values under the load of 100 N. Compared with pure PPS, the wear resistance of nano-micro porous PPS/PTFE composite was enhanced by 6.45 x 103 times, showing outstanding wear resistance. During sliding condition, grease could be squeezed through the nano-micro pores under the coupling effect of load and friction heat, and formed a lubricanting layer on friction surface, providing self-lubricating effect and high wear resistance. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013