Two osmium complexes of common formula [H(dmso)2][OsIVХ5(dmso‐κO)] 1 (Х=Cl) and 2 (Х=Br) are synthesized via the reaction of H2OsX6 (Х=Cl, Br) with DMSO. The complex 1 crystallized in the orthorhombic space group Pca21. For 2, two orthorhombic polymorphs are found, namely, 2 a in space group Cmcm and 2 b in space group Pbca. Within the [H(dmso)2]+ cations of 1 and 2 a, the cis‐configuration of the DMSO moieties has been observed for the first time. The complexes are characterized by a set of spectroscopic (NMR, IR, UV‐Vis, EXAFS/XANES) and diffraction (single crystal and powder) techniques. Both complexes 1 and 2 retain their molecular structures in DMSO and acetone solutions, as evidenced by Os L3‐edge EXAFS/XANES. 1H NMR spectra of 1 and 2 in DMSO solutions reveal signals of coordinated DMSO. In acetone solutions, signals of the [H(dmso)2]+ cations are observed in addition to those of coordinated neutral DMSO.

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