In this paper, Eu3+ beta-diketone Complexes with the two ligands 1-(2-naphthoyl)-3, 3, 3-trifluoroacetonate (TFNB) and 2'2-bipyridine (bpy) have been synthesized. Furthermore, we reported a systematical study of the co-fluorescence effect of Eu(TFNB)3bpy doped with inert rare earth ions (La3+, Gd3+ and Y3+) and luminescence ion Tb3+. The co-luminescence effect can be found by studying the luminescence spectra of the doped complexes, which means that the existence of the other rare earth ions (La3+, Y3+, Gd3+ and Tb3+) can enhance the luminescence intensity of the central Eu3+, which may be due to the intramolecular energy transfer between rare earth ions and Eu3+. The efficient intramolecular energy transfer in all the complexes mainly occurs between the ligand TFNB and the central Eu3+. Full characterization and detail studies of luminescence properties of all these synthesized materials were investigated in relation to co-fluorescence effect between the central Eu3+ and other inert ions. Further investigation into the luminescence properties of all the complexes show that the characteristic luminescence of the corresponding Eu3+ through the intramolecular energy transfers from the ligand to the central Eu3+. Meantime, the differences in luminescence intensity of the 5D0-->7F2 transition, in the 5D0 lifetimes and in the 5D0 luminescence quantum efficiency among all the synthesized materials confirm that the doped complex Eu(0.5)Tb(0.5)(TFNB)3bpy exhibits higher 5D0 luminescence quantum efficiency and longer lifetime than the pure Eu(TFNB)3bpy complex and other materials.