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The synthesis and physical properties of the double perovskite (DP) compound Ba2CdReO6with the 5d1electronic configuration are reported. Three successive phases originating from a spin-orbit-entangledJeff= 3/2 state, confirmed by a reduced effective magnetic moment of 0.72 μB, were observed upon cooling. X-ray diffraction measurements revealed a structural transition from a high-temperature cubic structure to a low-temperature tetragonal structure atTs= 170 K, below which theJeff= 3/2 state was preserved. Magnetization, heat capacity, a