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The asymmetric unit of the title compound, [Na2(C8H8O8)]n, contains one Na+ ion and half of a 2,3-bis(carboxymethyl)butanedioate (H2BTC2−) dianion, which lies on a center of symmetry. The dianion exhibits a μ10-bridging mode. Each Na atom lies in a NaO6 octahedron defined by six O atoms from five dianions. Adjacent NaO6 octahedra share a common O—O edge, generating a bioctahedron; adjacent bioctahedra are O—O edge-connected to one another, building up a chain along [001]. The chains are connected by adjacent H2BTC2− anions into a three-dimensional framework. The structure is further stabilized by O—H...O hydrogen bonds.