A new ligand, 1,1'-(pyridin-2,6-diyl)bis-3-p-tolylpropane-1,3-dione(H2L), was prepared and its crystal structure displays its enol isomer. The binary complex, Ln2L3·4H2O [Ln = Eu(III) and Tb(III)], were synthesized by the reaction of synthesized ligand (H2L) and Ln(III). With 1,10-phenanthroline (Phen) as the synergistic ligand, the ternary complex, Ln2L3(Phen)2 [Ln = Eu(III) and Tb(III)], were synthesized. The compounds were characterized by 1H-NMR spectroscopy, MS, IR, UV, DTA-TG and fluorescence spectrum. The luminescent properties of the ligand and its complexes were investigated and the results showed that the prepared ligand was a good luminescent compound, all complexes emitted characteristic luminescence of corresponding lanthanide ions and 1,10-phenanthroline as the synergistic ligand can obviously enhance the luminescence of Eu(III) in the ternary complex.