Summary: The Si-Si bond of disilanes is found to be cleaved by tetrabutylammonium fluoride (TBAF) in hexamethylphosphoric triamide to produce metal-free silyl anion and triorganosilyl fluoride. The disilane/TBAF reagent was studied spectrometrically. Synthetic application of the reagent with a catalytic amount of TBAF is illustrated by the reaction with aldehydes and 1, 3-dienes.