Selective bridgehead chlorination of permethylbicyclo [2.2. 2] octasilane 1 giving the corresponding 1-chloro-(2a) and 1, 4-dichlorobicyclooctanes 3a was achieved using BCl 3 in chloroform. 1-Chlorobicyclooctane 2a resists the reactions with various nucleophiles such as phenyllithium and lithium aluminum hydride but reacts with KC 8 affording the corresponding silylpotassium 2b in quantitative yield.