The nature of the SH⋅⋅⋅S hydrogen-bonding interaction in the H2S dimer and its structure has been the focus of several theoretical studies. This is partly due to its structural similarity and close relationship with the well-studied water dimer and partly because it represents the simplest prototypical example of hydrogen bonding involving a sulfur atom. Although there is some IR data on the H2S dimer and higher homomers from cold matrix experiments, there are no IR spectroscopic reports on SH⋅⋅⋅S hydrogen bonding in the gas phase to-date. We present experimental evidence using VUV ionization-detected IR-predissociation spectroscopy (VUV-ID-IRPDS) for this weak hydrogen-bonding interaction in the H2S dimer. The proton-donating SH bond is found to be red-shifted by 31 cm−1. We were also able to observe and assign the symmetric (ν1) stretch of the acceptor and an unresolved feature owing to the free SH of the donor and the antisymmetric (ν3) SH stretch of the acceptor. In addition we show that the heteromolecular H2S–MeOH complex, for which both SH⋅⋅⋅O and OH⋅⋅⋅S interactions are possible, is S-H⋅⋅⋅O bound.