Extraction of unbound materials from carbon-black-filled natural rubber (NR) vulcanizates with different cure systems was studied using various solvents with different dielectric constants of n-hexane, toluene, THF, acetone, and acetonitrile. The extraction was performed at room temperature and 40 degrees C for 2 days and in the boiling solvent for 8 h. Amounts of extracted materials from the NR vulcanizates increase by increasing the temperature. Amounts of extracted materials from the NR vulcanizates with n-hexane, toluene, and THF are more than those with acetone and acetonitrile. Amounts of extracted materials from the NR vulcanizate with a high crosslink density are less than those from the NR vulcanizate with a low one. Thermogravimetric analysis of the NR vulcanizates before and after the extraction were carried out to investigate components of the extracted materials. It was found that there were polymer components and metal complexes, as well as organic matters with a low molecular weight in the extracted materials. Abilities of the solvents to extract unbound materials from the NR vulcanizates were discussed.