The ultrathin multilayer films of rare-earth-containing polyoxometalate cluster K17[Eu(P2Mo17O61)2](EuPMo) and poly(allylamine hydrochloride)(PAH) have been prepared by the Layer-by-Layer(LbL) self-assembly method. The photoluminescent behavior of the films investigated at room temperature shows the Eu3+ characteristic emission pattern of 5D0→7FJ(J=1-4). The occurrence of the photoluminescent activity confirms the potential of creating luminescent multilayer films with polyoxometalates(POMs).