Microwave spectra of methylsilanethiol and three of its deuterated species were measured and assigned for the gauche and trans isomers. The double minimum splitting due to internal rotation of the mercapto group in the gauche isomer was directly observed in c-type transitions for all the species measured. Rotational constants and the pure torsional energy difference, Δ ν, between the (+) and (−) states in the gauche isomer of the parent species were determined to be A(+) = 15 567.654 ± 0.040, B(+) = 3663.038 ± 0.004, C(+) = 3179.727 ± 0.005, Δ A = −4.328 ± 0.021, Δ B = −0.220 ± 0.012, Δ C = −0.008 ± 0.011, and Δ ν = 2826.371 ± 0.045 MHz, where A(+) represents the A rotational constant of the (+) state and Δ A = A(−) – A(+) and so on. For the trans isomer of the parent species, the following rotational constants were determined: A = 14 745.953 ± 0.051, B = 3841.291 ± 0.010, C = 3220.350 ± 0.010. Additional splittings due to internal rotation of the methyl group were also observed for both of the isomers. Analysis of these splittings derived barrier heights of the methyl internal rotations to be 1581 ± 26 and 1729 ± 23 cal/mol for the trans and gauche isomers of the parent species, respectively. Dipole moments were obtained from Stark effect measurement to be 1.056 ± 0.006 and 1.604 ± 0.006 D for the trans and gauche isomers of the parent species, respectively. Potential function of the mercapto internal rotation and plausible structures for both the isomers were discussed.