The title compound, [Na₂(C₆H₅N₂O₂)₂(C₆H₆N₂O₂)₄], is a centrosymmetric coordination dimer based on the sodium(I) salt ofN-hydroxypicolinamide. The molecule has an {Na₂O₆(μ-O)₂} core with two bridging carbonyl O atoms and two hydroxamate O atoms of two mono-deprotonated residues ofN-hydroxypicolinamide, while two neutralN-hydroxypicolinamide molecules are coordinated in a monodentate manner to each sodium ionviathe carbonyl O atoms [the Na—O distances range from 2.3044 (2) to 2.3716 (2) Å]. The pentacoordinated sodium ion exhibits a distorted trigonal–pyramidal coordination polyhedron. In the crystal, the coordination dimers are linked into chains along thecaxisviaN—H...O and N—H...N hydrogen bonds; the chains are linked into a two-dimensional framework parallel to (100)viaweak C—H...O and π–π stacking interactions.