The title complex, [Li2(C(6)H(3)N(2)O(5))2(H2O)4], contains two kinds of Li atoms, viz. five-coordinated and four-coordinated. The five-coordinated Li ion has a tetragonal-pyramidal geometry, with a water molecule in the apical position and four O atoms from two 2,4-dinitrophenolate (2,4-DNP) ligands in the basal plane. The four-coordinated Li ion has a tetrahedral geometry, with three water molecules and one phenolate O atom of a 2,4-DNP ligand. The Li ions are bridged by a phenolate O atom, giving the complex a dinuclear structure. The crystal packing is stabilized by O-H...O hydrogen-bonding interactions involving the water molecules and nitro O atoms.