The organopolysilanes Me(Me2Si)nMe (n = 4–6), (Me2Si)6 and (Me3Si)2SiMePh are found to be effective photoinitiators for the polymerization of vinyl‐containing siloxane rubbers. The trisilanes Me(ME2Si)3Me and Me3SiSiMe2SiMe2Ph are slightly effective, while phenyldisilanes do not exhibit initiation activity in the process of photocuring. Polydimethylsiloxanes are cured at a slower rate under the same conditions than vinylcontaining derivatives. Two mechanisms of crosslinking are proposed: silylene–silirane–silanol and silylene–hydride–silanol.