Abstract The chemical compounds carrying the thiol group (-SH) have been considered essential in recent prebiotic studies regarding the polymerization of amino acids. We have searched for this kind of compound toward the Galactic Center quiescent cloud G+0.693–0.027. We report the first detection in the interstellar space of the trans-isomer of monothioformic acid (t-HC(O)SH) with an abundance of ∼1 × 10⁻¹⁰. Additionally, we provide a solid confirmation of the gauche isomer of ethyl mercaptan (g-C₂H₅SH) with an abundance of ∼3 × 10⁻¹⁰, and we also detect methyl mercaptan (CH₃SH) with an abundance of ∼5 × 10⁻⁹. Abundance ratios were calculated for the three SH-bearing species and their OH analogs, revealing similar trends between alcohols and thiols with increasing complexity. Possible chemical routes for the interstellar synthesis of t-HC(O)SH, CH₃SH, and C₂H₅SH are discussed, as well as the relevance of these compounds in the synthesis of prebiotic proteins in the primitive Earth.