Microwave spectra were observed and analyzed for 2-aminoethanethiol and 2-chloroethanethiol. The amino compound exists in two gauche rotameric conformations, one exhibiting an intramolecular SH⋯N hydrogen bond. The hydrogen-bonded conformer lies higher in energy by 274 ± 90 cal mole −1 and has the following rotational constants (in MHz): A = 12 040.1 ± 11.3, B = 3352.24 ± 0.03, and C = 2881.99 ± 0.03. For the non-hydrogen-bonded conformer the rotational constants (in MHz) are A = 11 929.9 ± 10.2, B = 3395.01 ± 0.03, and C = 2877.82 ± 0.03. Dipole moment measurements for the H-bond conformer led to μ a = 2.68 D, μ b = 0.88 D, and μ c = 0.37 D, while for the non-H-bond form the values are μ a = 1.51 D, μ b = 0.0 D, and μ c = 0.62 D. In the case of chloroethanethiol, the only assigned spectral lines were the unresolved J → J + 1 a-type bands of a trans conformation. For this molecule the combination rotational constant B + C has the value 2955.17 ± 0.02 MHz for the 35Cl species and 2879.73 ± 0.02 MHz for the 37Cl species.