A series of europium(III) complexes of 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen) were synthesized. The new complexes Eu(TPA)(TTA)Phen and Eu-2(TPA)(TTA)(4)Phen(2) were characterized by elemental analysis, IR spectrum, scanning electron microscope and thermal stability analysis. The results show that the thermal stability of the Eu(III) complexes increases in the following order: the mononuclear complex Eu(TTA)(3)Phen, the binuclear complex Eu-2(TPA)(TTA)(4)Phen(2), the chain polynuclear complex Eu(TPA)(TTA)Phen. And the formation of the binuclear/polynuclear structure of the new complexes appears to be responsible for the enhancement of their thermal and optical stability. In addition, The fluorescence excitation spectra of these new complexes show more broad excitation bands than that of the complex Eu(TTA)(3)Phen corresponding to their formation. The enhancement of Eu3+ fluorescence in the new complexes can be observed by the addition of Gd3+. The bright red luminescent plastics can be obtained when the complex EuGd(TPA)(TTA)(4)Phen(2) is added above 0.5% (mass fraction).