The interaction of H2S with HKUST-1 and ZIF-8 MOFs has been studied by means of FT-IR, Raman, DRUV-Vis-NIR and PXRD techniques. At very low equilibrium pressure (below 5 mbar) a stepwise structural distortion is observed in both HKUST-1 and ZIF-8. At higher equilibrium pressures (20–60 mbar), PXRD technique, in particular, showed the structural destruction of HKUST-1 with formation of a covallite (CuS) phase and some structural distortion of ZIF-8.