A general approach to the functionalization of aliphatic C-Si bonds in the presence of silver salts and oxidants has been reported. This strategy encompasses a range of valuable C-Si transformations, including the direct conversions of a C-Si bond to C-OCF3, C-OBz, C-OCOCF3, C-SCF3, C-SCN, and C-N3 bonds. Among them, trifluoromethoxylation of alkylsilanes is reported for the first time. In addition, mechanistic studies indicate that this reaction may proceed through a radical mechanism.