Tribological properties at high temperature are an important research aspect for high speed or heavy load situation. This paper is to study the structure effects on the tribological properties of Cu–SiC foam ceramic (SiCf) composites at high temperature. Cu-SiCf composites form two interconnected three-dimensional (3D) network structure, which tribological properties could be controlled by designing SiCf ceramic volume fractions, friction components and mesh size. The results showed that SiCf ceramic has overall enhancement mechanism to Cu alloy and friction components by 3D-structure. Additionally, Cu-SiCf composites have friction properties of high temperature resistance, low wear rate, and stable coefficient of friction (COF).