Abstract Triisopropylsilanethiol (HSTIPS, 1), easily prepared in 98% yield from H 2 S and TIPSCl, is efficiently alkylated in a selective manner with 1 and 2 alkyl halides or tosylates through its potassium thiolate (2c) to provide RSTIPS (3) in excellent yields. Compound 3 provides a convenient source of alkanethiols (4), unsymmetrical dialkyl sulfides (5) and thioacetals (6).