The 1-hydro-1-lithio-silafluorene anion 2 has been isolated and characterized by single-crystal X-ray analysis for the first time. Three tetrahydrofuran molecules coordinate with lithium atoms in the crystal structure of 2. 2 was reacted with a number of electrophilic reagents and it can be used as a useful reagent for generating various functional hydrogen-substituted silafluorenes. Treatment of 2 with 2 equiv. of chlorobis(isopropyl)phosphine afforded chloro-substituted silafluorene 4. The reaction of 8 which has a SiH-SiBr fragment with IiPr2Me2 (IiPr2: 2,5-diisopropyl-3,4-dimethylimidazol-1-ylidene) led to the formation of an Si-Si bond cleavage product, NHC-stabilized silacyclopentadienylidene 9.