A procedure to synthesize (μ-hydroxo)bis-pentaaquarhodium(III) nitrate tetrahydrate [Rh2(H2O)8(μ-OH)2](NO3)4·4H2O from potassium hexachlororhodiate(III) is elaborated. The compound is isolated into the solid phase and structurally characterized. The crystallographic data are as follows: a = 5.8763(2) Å, b = 9.4749(4) Å, c = 9.6249(3) Å, α = 79.905(1)°, β = 84.324(1)°, γ = 82.922(1)°, space group P-1, Z = 1, ρcalc = 2.240 g/cm3. The compound is soluble in water, ethanol, and acetone. Hydrolysis takes place in concentrated nitric acid with the formation of mononuclear aqua- and aquanitrate complexes. Thermal decomposition of the salt at a temperature above 580 °C leads to the formation of a single product–rhodium(III) oxide.