Perfluoroelastomeric articles were cross-linked by electron beam irradiation. Irradiation experiments were carried out on the pure polymer free of fillers, processing aids, or curing chemicals. Doses of 10-15 Mrads are adequate to give gel content of >95%. The compression set, tensile strength, and chemical resistance of O-rings thus crosslinked are very good and comparable to those of chemically cross-linked ones. There is little difference in terms of efficiency of cross-linking and properties among perfluoroelastomers containing various functionalities, such as nitrile, iodine, bromine, hydrogen, and perfluorbenzene. In addition to cross-linking, irradiation causes structural changes, such as formation of acid fluorides on the polymeric chain ends as a result of main-chain scissions and generation of small amounts of volatile products (CF4, COF2, CO2, CF3OCF3) attributed to side-chain scissions. The cross-links appear to be thermally and chemically stable carbon-carbon bonds.