Today, the modification of carbon foam for high performance remains a major issue in the environment and energy industries. One promising way to solve this problem is the optimization of the pore structure for desired properties as well as for efficient performance. In this study, using a sol-gel process followed by carbonization in an inert atmosphere, hollow spherical carbon foam was prepared using resorcinol and formaldehyde precursors catalyzed by 4-aminobenzoic acid; the effect of carbonization temperature and re-immersion treatment on the pore structure and characteristics of the hollow spherical carbon foam was investigated. As the carbonization temperature increased, the porosity and average pore diameter were found to decrease but the compression strength and electrical conductivity dramatically increased in the temperature range of this study (700˚C to 850˚C). The significant differences of X-ray diffraction patterns obtained from the carbon foams carbonized under different temperatures implied that the degree of crystallinity greatly affects the characteristics of the carbon form. Also, the number of re-impregnations of carbon form in the resorcinol-formaldehyde resin was varied from 1 to 10 times, followed by re-carbonization at 800˚C for 2 hours under argon gas flow. As the number of re-immersion treatments increased, the porosity decreased while the compression strength improved by about four times when re-impregnation was repeated 10 times. These results imply the possibility of customizing the characteristics of carbon foam by controlling the carbonization and re-immersion conditions.