The rotational spectrum of the 36 S-bearing isotopologue of hydrogen sulfide (H 2 S) has been investigated for the first time in the 167 GHz−1.6 THz frequency range, thus providing an accurate and reliable set of spectroscopic parameters. The experimental investigation was backed up by state-of-the-art quantum-chemical calculations, which also allowed us to demonstrate the incorrectness of the previously reported spectroscopic constants. The present results are of suitable accuracy to attempt the astrophysical detection of the isotopic species under consideration. Finally, reliable predictions for the spectroscopic constants of other rare isotopologues of H 2 S, namely the mono-and bi-deuterated species containing 33 S and 34 S, are provided.