Carbon nanotube/expanded graphite composite material was prepared by expanding the mixture of multi-walled carbon nanotubes and expansible graphite under the condition of high temperature. The microstructure and composition was studied by using SEM and XRD. The study shows that the tubular structure of carbon nanotubes in the composite material is changed by high temperature expanding process, and the microstructure is different with different expanding temperature. When the expanding temperature was 900°C, carbon nanotubes transformed, then attached to the surface of expanded graphite flake, so carbon nanotubes and expanding graphite combined strongly; globular carbon nanotubes attached to the surface of expanded graphite flake at the temperature of 700°C, both were combined much more strongly; carbon nanotubes retained the tube structure at the temperature of 500°C, combination was looser due to the simple physical adsorption. The result shows that the choice of expanding temperature has an important effect on microstructure of carbon nanotube/expanded graphite composite material.