In this study, the effect of single-walled carbon nanotubes (SWCNTs) on the cross-linking of natural rubber (NR) using organic peroxides was investigated. NR-SWCNTs nanocomposites were prepared in an open two-roller mill followed by vulcanization with the compression molding process. Three different organic peroxides, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (T29), dicumyl peroxide (DCP), and 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne (T145), were used as vulcanizing agents. SWCNTs promote a remarkable reduction in the vulcanization time and increase the degree of cross-linking of vulcanized rubber when compared with neat or natural rubber–carbon-black composites; the same tendency was obtained in the NR-SWCNTs vulcanized with sulfur. Additionally, the mechanical performance of the NR-SWCNTs composites was significantly improved up to 75, 83, 27, and 10% for tensile strength, moduli, tear strength, and hardness. Raman spectroscopy studies evidence the occurrence of reaction between nanotube walls and free radicals generated from using organic peroxides during the vulcanization process. These results demonstrate that the incorporation of SWCNTs in combination with the use of organic peroxides for the NR vulcanization represents a potential alternative for the improvement of the physicochemical properties of NR composites.