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The dinuclear Mn^III complex [Mn₂O(PhCOO)₂(bpy)₂(OH)(NO₃)]·H₂O was prepared by controlled oxidation of manganous nitrate with n-tetrabutylammonium permanganate in the presence of benzoic acid (PhCOOH) and 2,2‘-bipyridine (bpy). Its structure was determined in a single-crystal X-ray diffraction experiment, and consists of a triply-bridged [Mn₂(μ-O)(μ-PhCOO)₂]²⁺ dinuclear core. Each manganese(III) ion bears a chelating bpy and a terminal X anion (X = OH^- or NO₃^-) completing a distorded octahedral coordination geometry. Although the terminal anions are located in disordered positions, the analysis of bond lengths and steric considerations led us to assign to the complex an asymmetric structure [(bpy)(OH)Mn^III(μ-O)(μ-PhCOO)₂Mn^III(bpy)(ONO₂)]. The product, with a chemical formula C₃₄H₂₉Mn₂N₅O₁₀, crystallizes in the monoclinic system, space group C2/c, with a = 16.607(4) Å, b = 25.619(6) Å, c …