We obtained the Eu(TTA)3phen•H2O-PVP composite film by rare earth complexes Eu(TTA)3 phen•H2O was doped intentionally in polyvinylpyrrolidone(PVP), and the factors of effect it’s luminous intensity were investigated. The results indicate that the luminous effect of sample was best when the water and the alcohol proportion is 1: 4 in the resolver, the aggregation-time reached 12 h and the doping concentration of europioun ion reached 0.6%. The infrared spectrum analyses of sample indicate that there is an interaction between Eu(TTA)3phen•H2O and PVP. In addition, the fluorescence spectra and ultraviolet spectrum analyses of sample indicate that polymer materials can not only fix rare earth ions to enhance its luminescence intensity, but also avoid the quenching effect to rare earth caused by water molecule, through the replacement of PVP ligand to water molecule in the complex. The luminous intensity of the rare earth complexes can be greatly enhanced, and the composite film contained high amount of rare earth complexes is obtained, which laid a foundations for further study the film formation properties of rare earth complexes luminous materials.