The highly reactive silyl triflates R_4-nSi(OSO₂CF₃)_n are valuable materials in organosilicon chemistry. Numerous new triflate derivatives of mono-, oligo- and polysilanes were prepared by stepwise substitution of trifluoromethanesulfonyl groups for phenyl groups or other leaving groups. Conversions of silyl triflates with nucleophiles proceed regioselectively and, in most cases, quantitatively at low temperatures with short reaction times. Therefore, silyl triflates are suitable reagents for the synthesis and functionalization of linear and cyclic oligosilanes. Novel polycarbosilanes, polysilylalkynes, and polysilylphenylenes, which show a regular alternating arrangement of silylene groups and organic units, were prepared from α,ω- bis[(trifluoromethyl)sulfonyloxysilyl]-substituted compounds and dinucleophiles. Branched polysilanes and polysilynes were obtained by reductive coupling of polymeric silyl triflates with potassium-graphite.