Abstract: Transition metal-free radical hydrosilylation of alkynes and factionalized alkenes to vinylsilanes, organosilanes from alkenes, radical silylative cyclizations for sila heterocycles, aromatic dehydrogenative radical silylation, sila-amino acids, silyl hydroperoxides by using transition metal-free reaction conditions such as peroxides, photocatalyst, hydrogen atom transfer catalyst, radical initiators have become one of the most important and useful methodologies for the construction of C-Si bonds for their synthetic applications. In order to demonstrate the growth in this area, this review highlights the last twenty years of success in the fields of silylation of aromatics, silylative cyclizations of sila heterocycles, synthesis of vinylsilanes by hydrosilylation of alkynes, and functionalized alkenes, organosilanes from alkenes and dehydrogenative approaches for vinylsilanes involving radical mechanisms. We believe that summarizing these methods would be very useful for the chemists who are interested in the synthesis of organosilicon compounds for drug discovery or the development of silicon-based materials for industrial applications.