Due to the versatile transforming ability of C–B and C–Si bonds, gem-borylsilylalkanes have emerged as powerful reagents and attracted increasing attention in synthetic chemistry, and great efforts have been made to access these motifs from easily accessible chemical feedstocks. Besides, compared with gem-diborylalkane analogues, gem-borylsilylalkanes can be chemoselectively converted into various functionalized molecules through selective C–Si and C–B bond transformation. This review summarizes the recent development in the synthesis of gem-borylsilylalkanes as well as their chemoselective transformation.