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In the title compound, [Nd2(C6H3BrNO2)6(H2O)4]·2H2O, the NdIII ion is coordinated by nine O atoms from one chelating 5-bromonicotinate ligand, four bridging 5-bromonicotinate ligands and two water molecules, exhibiting a distorted three-capped triangular-prismatic geometry. Two NdIII ions are bridged by four carboxylate groups in bi- and tridentate modes, forming a centrosymmetric dinuclear unit, with an Nd...Nd distance of 4.0021 (5) Å, and intramolecular π–π interactions between the pyridine rings [centroid–centroid distance = 3.960 (2) Å]. Intermolecular π–π interactions [centroid–centroid distances = 3.820 (2) and 3.804 (2) Å] and O—H...N and O—H...O hydrogen bonds connect the dinuclear molecules into a three-dimensional supramolecular network.