Abstract A visible‐light‐induced strategy utilizing sulfur hexafluoride (SF 6 ) as distinctive oxidant and water as the oxygen source to transform silanes into siloxanes has been developed under mild conditions, realizing the efficient utilization and degradation of the strong greenhouse gas, sulfur hexafluoride, simultaneously. Mechanistic experiments demonstrate that the reaction proceeds through a radical pathway, and it has been confirmed that the oxygen atoms in the resulting siloxanes indeed originate from water by isotopic labeling experiments with 18 O.