In this article, low-density polyethylene (LDPE) rubber and silica (SiO₂) particles were employed to modify polytetrafluorethylene (PTFE) simultaneously. The distribution and dispersion of LDPE and SiO₂ particles in PTFE matrix can be adjusted by the wettability of SiO₂ particles toward PTFE and LDPE, so as to achieve a simultaneous enhancement of toughness and modulus of PTFE. A unique structure with the majority of PTFE surrounded by SiO₂ particles was first observed using maleic anhydride (MAH)-grafted LDPE, resulting in a dramatical increase in Izod impact strength as the rubber content in the range of brittle–ductile transition (4–16 wt%). The friction and wear properties were obviously improved with the addition of MAH-grafted LDPE regardless of the content of SiO₂.