Novel photoluminescent films consisting of three-dimensionally ordered macroporous (3DOM) SiO2:Tb3+ and Au nanoparticles were prepared by template assisted method, and their luminescence properties were investigated. The results show that Au nanoparticles have significant influence on luminescence property of SiO2:Tb3+ 3DOM materials. The Au nanoparticles embedded in the skeleton of SiO2:Tb3+ 3DOM materials could strongly improve their luminescence properties. The enhancement mechanism was discussed and demonstrated, which is attributed to the increasing of radiative decay rates of Tb3+ induced by surface plasmon effects of Au nanoparticles.