This study improved the tribological property of epoxy composite by filling carbon fiber-carbon nanotube multiscale hybrid synthesized via the non-corrosive LaCl3 surface treatment method. In the tribological study of composites, the friction process was divided into four stages with the revealing of corresponding mechanisms, and the initial friction process was investigated based on surface analysis results. Notably, the reductions in friction coefficient (81.8%) and wear rate (97.6%) of hybrid reinforced composite distinguish this study from other similar researches, which is due to the lowered surface adhesion and strengthened interfacial property that prevents fiber debonding and avoids three-body abrasive wear. Also, this study analyzed the tribological characteristics of epoxy composite under different reciprocating frequency and load.