The synthesis and structural characterization of tetra(1H, 1H, 2H, 2H-polyfluoroalkyl)silanes with the same or different chain lengths CnF2n+1 linked to Si (1 less-than-or-equal-to n less-than-or-equal-to 6) is reported. When the synthesis was effected from chlorosilanes and fluorinated organomagnesium or organolithium reagents, the trialkylsilanes were obtained. The last fluorinated chain was introduced either via a fluoroalkyllithium reagent or by hydrosilylation of the trialkylsilanes. Some properties and characterization by H-1, F-19 and Si-29 NMR spectroscopy of the 1H,1H,2H,2H-polyfluoroalkylsilanes are described.