A new method was developed for the metal-free cross-linking of silicone rubbers. This process uses azobisisobutyronitrile (AIBN) to selectively react with Si-H and vinyl groups as a free-radical initiator for the thermal curing of polymethylhydrosiloxane (PMHS) and polymethylvinylsiloxane (PMVS). The AIBN-initiated curing reaction between the Si-H groups of PMHS generated Si-O-Si and Si-Si cross-links. In contrast, PMVS was cured via the formation of C-C bonds through "methyl-vinyl"and "vinyl-vinyl"mechanisms. Curing reactions were performed at 80-120 °C in air and confirmed by 13C and 29Si solid state NMR analyses and swelling trials.