The three-dimensional ordered macroporous (3DOM) LaPO4: Eu3+ films and Ag nanoparticles (NPs) were prepared via a template-assisted process and sodium citrate reduction method, respectively. Composite systems consisting of 3DOM LaPO4: Eu3+ films and Ag NPs were obtained by adding the Ag NPs into voids of 3DOM LaPO4: Eu3+ films. The influence of Ag NPs on photoluminescence of 3DOM LaPO4: Eu3+ was investigated. The results show that photoluminescence properties of 3DOM LaPO4: Eu3+ films were enhanced after addition of Ag NPs, which was attributed to the local surface plasmons resonance effect of Ag NPs.