Two barium hexafluoridoosmates, Ba(OsF6)2 and BaOsF6, were synthesized and were characterized for the first time using X-ray powder and single crystal diffraction, IR spectroscopy, as well as NMR spectroscopy in anhydrous hydrogen fluoride. Ba(OsF6)2 crystallizes in the space group type P21/c with the cell parameters a = 6.4599(4), b = 10.7931(8), c = 14.7476(10) Å, β = 115.195(5)°, V = 930.42(12) Å3, Z = 4 at 293 K. BaOsF6 crystallizes in the space group type R 3 ¯ with the cell parameters a = 7.3286(10), c = 7.2658(15) Å, V = 337.95(12) Å3, Z = 3 at 100 K. Additionally, we have obtained the compounds Ba(OsF6)2∙3BrF3, Ba(OsF6)2∙HF, Ba(OsF6)2∙6H2O from the respective solvents, and Ba(OsF6)2.