On the basis of the ligamental reticulated carbon foam by Klett in 2000 and hollow microsphere carbon foam by Bruneton in 2002, a hollow microsphere/ reticulated composite carbon foam is prepared by microstructural optimization, carbonization and graphitization sequentially. The scanning electron microscope (SEM) and stereo microsccope tests demonstrate that both reticulated ligament and globe cavity show obvious spacial periodicities. Diffraction peak of X-ray diffraction (XRD) at 26°indicates that the sample features graphitization. Besides, the forming mechanism is also analyzed.