The reactions of gamma-SO3 with the silanes R(f)Si(CH3)(3) [R(f) = CF3 (1), C6F5 (2), CF2=CF (3), CF2=CFCH2CH2 (8), and R(f)Si(n-C3H7)(3) [R(f) = CF2=CF (7), CF2=CFCH2CH2 (9)] are reported. Several of the expected silyl sulfonates R(f)SO(2)OSi(CH3)(3) [(R(f) = CF3 (4), C6F5 (5), CF2=CF (6)] are isolated. The polyfluoroalkenyltin compound CF2=CFCH2CH2Sn(CH3)(3) (10) is prepared, and also reacted with gamma-SO3; however, the tin sulfonate does not form. With fluorinated siloxanes R(f)OSi(CH3)(3) [R(f) = (CF3)(2)CH (11), (CF3)(2)C(CH3) (12), (CF3)(2)C(C6H5) (13), CF3CH2 (14), (CF3)(3)C (15), (CH2CF2)(2) (16)] reactions with gamma-SO3 give the respective silyl sulfate esters R(f)OSO(2)-OSi(CH3)(3) in yields up to 85%. The acids CF2=CFSO3H (25) and (HO3SOCH2CF2)(2) (26) are easily obtained by the hydrolysis of 6 and 22, respectively. The compounds prepared in this study are characterized by H-1, F-19 and Si-29 NMR, IR and mass spectrometry.