For the phase of H2S under a pressure larger than 110 GPa high temperature superconductivity has been reported [1] with Tc of 200 K. The decomposition of H2S into SH3 + S under such conditions has been deduced from synchrotron x-ray diffraction (XRD) experiments. [ 2 , 3 , 4 ] The obtained XRD patterns can be indexed based on a mixture of two phases, namely, the bcc m Im3 structure ascribed to H3S with cell parameter a = 3.089 Å and the -Po structure of sulfur. [3,5 ] Another XRD study under high pressure reported a more complex decomposition mixture that includes H3S and H4S3 phases. [6] DFT calculations confirmed the proposed m Im3 structure of H3S as the lowest energy one. [2,7,8,9,10,11] The m Im3 structure of H3S (a = 3.089 Å) consists of two interpenetrating SH3 perovskite sublattices ( Figure 1a)) with a HH contact distance of 1.5 Å, which is very short compared with the van der Waals radii sum of 2.4 Å but very long compared with the HH single-bond distance 0.74 Å in H2. The decomposition, 3 H2S 2 H3S + S, implies that the XRD intensities of H3S and sulfur with -Po structure should have a 2:1 ratio. However, the comparison of the simulated XRD patterns with the observed ones taken from the literature in Figure S1 of the supporting information (SI) shows that the amounts of S in the samples vary and are always substantially smaller or hardly detectable than the expected one. Except for some spurious reflections the XRD patterns belong to a bcc lattice of sulfur atoms, but are not adequate enough to refine and assign the hydrogen atom positions with the Rietveld method. The bcc pattern is plotted in red color in Figure S1. The diagram in green color corresponds to sulfur with β-Po structure that should form in the decomposition reaction 3 H2S 2H3S + S, however, sulfur does not show up except for one weak reflection at 2 = 12°. Thus the formation of H3S itself is questionable. The abovementioned inconsistencies together with the apparent analogies between H2S and H2O were our motivation to reinvestigate the structure of the superconducting phase obtained from H2S under ultrahigh pressure. Figure 1 b). On the basis of DFT calculations, [14,15,16] we show that the perovskite (SH -)(H3S + ) is thermodynamically more favorable than H3S. In view of the expected dynamic motions of hydrogen, one can imagine that the functionalities of the S atoms on the A and B sites of the perovskite ABO3 can easily be interchanged, according to (SH -)(H3S + ) (H3S + )(SH -). In addition, our calculations reveal that at every A-site of a perovskite (SH -)(H3S + ) the SH bonds orient preferentially toward any one of the six faces of the S8 cube, as shown in Figures 1c) and d). In case of all A-site S-H bonds pointing in one direction, the optimization of the crystal structure of (SH -)(H3S + ) results in an arrangement of four H atoms of the H3S + sublattice with short HH contacts. These H atoms are displaced away from the H atom of the SH bond ( Figure 1c) (for the cif files of this P4mm structure, see SI...