The regiospecific ring-opening of both mono- and disubstituted epoxides with trusopropylsilanethiol/DBU has been developed to provide 2-trusopropylsilyloxyalkylthiols (1) in high yields. Non-racemic 1 is easily prepared from optically active epoxides. Moreover, the further elaboration of 1, through the exposed mercapto functionality, provides controlled access to unsymmetrical mono-protected bis-(2-hydroxyalkyl) sulfides and functionalized thioesters.