SiHbonds can be activated by organozinc and silylzinc compounds in the presence of minute amounts of radical initiators such as tBu2Hg or AIBN, yielding zinciosilanes in good yields (see scheme). Activation of dihydridosilanes leads to geminal dizinciosilanes. Zincio‐bridged disilyllithium compounds, which have three (1) and four metal–silicon bonds, were also synthesized.