Two novel pyridine-2,6-dicarboxylic acid derivatives of mono-β-diketone, methyl 6-benzoylacetyl-2-pyridinecarboxylate (MBAP) and 6-benzoylacetyl-2-pyridinecarboxylic acid (BAPA) and their Eu(III) and Tb(III) complexes were synthesized and characterized by elemental analysis, FT-IR, 1H NMR and TG–DTG. Moreover, their Eu(III) and Tb(III) complexes using 1,10-phenanthroline as a secondary ligand were prepared and characterized. The luminescence properties of these complexes in solid state were investigated in detail. The results suggested that Tb(III) complexes exhibit more efficient luminescence than Eu(III) complexes, the fluorescence intensity of Ln(III) complexes with BAPA is about twice as strong as that of Ln(III) complexes with MBAP, the fluorescence of mono-β-diketone complexes using 1,10-phenanthroline as a secondary ligand was prominently higher than that of complexes without adding 1,10-phenanthroline, and the ligand BAPA is an excellent sensitizer to Eu(III) and Tb(III) ion.