The process was discovered in 1839 by the U.S. inventor Charles Goodyear (Goodyear, Charles), who also noted the important function of certain additional substances in the process. Such a material, called an accelerator (q.v.), causes vulcanization to proceed more rapidly or at lower temperatures. The reactions between rubber and sulfur are not fully understood, but in the product, the sulfur is not simply dissolved or dispersed in the rubber; it is chemically combined, mostly in the form of cross-links, or bridges, between the long-chain molecules.

In modern practice, temperatures of about 140°–180° C are employed, and in addition to sulfur and accelerators, carbon black or zinc oxide is usually added, not merely as an extender, but to improve further the qualities of the rubber. Anti-oxidants are also commonly included to retard deterioration caused by oxygen and ozone. Certain synthetic rubbers are not vulcanized by sulfur but give satisfactory products upon similar treatment with metal oxides or organic peroxides.