The exchange interaction of lanthanum and some lanthanides salts (neodymium, samarium, europium, gadolinium, terbium and dysprosium) with sodium salt of 2,4-dichlorophenoxyacetic acid (HL) in dimethylformamide medium produced lanthanum and lanthanide carboxylates. The compounds were studied by elemental and thermal analysis, infrared spectroscopy and X-ray structure analysis. It was found that the complexes form two isostructural series: [Ln2L6(DMF)3]∙Solv (Ln = La, Nd, Sm, Eu) and [LnL3(H2O)2]∙2DMF∙Solv (Ln = Gd, Tb, Dy). Both series have a one-dimensional polymer structure in which the central atoms are connected by bridging carboxylate anions. The crystal structures of the complexes have a branched network of noncovalent D-H…A and Cl…Cl interactions. An analysis of the photophysical properties of all compounds revealed a bright luminescence with a quantum yield up to 39.5 % and an excited state lifetime of 1330 μs for the europium polymer enhanced by 2,4-dichlorophenoxyacetate ligands.