The PEEK fabric-reinforced polyimide resin containing microcapsules with excellent mechanical and lubrication properties is reported. The GO-COOH/TiO2@PAO double-wall microcapsules (Capsule) were prepared by interfacial condensation polymerization of titanium butoxide (TBT) and self-assembly between GO-COOH and TiO2 shell. A double crosslink of chemical bond (amide or ester) and hydrogen bond were constructed between microcapsules and polyimide (PI) to improve the mechanical properties of PEEK fabric-reinforced polyimide resin (PEEK/PI). It was identified that the addition of Capsules induced a 12.98% decrease in friction coefficient and 56.85% in the wear rate of the composites. This superior frictional behavior was primarily attributed to the combined effect of the boundary lubrication of PAO6, load-bearing effect of TiO2 and PEEK fabric, and friction-reducing of GO-COOH.