The　red　phosphor　Na5Eu(WO4)4　activated　with　trivalent　M3+　(M3+　=　Bi3+,　Sm　3+)　ions　were　prepared　through　the　solid　state　reaction　technique.　The　properties　of　structure,　morphology,　photoluminescence　were　characterized　systematically.　The　lattice　parameters　were　refined　by　Rietveld　method.　The　emission　spectra,　excitation　spectra,　and　decay　curves　were　employed　to　study　the　luminescent　behaviors.　Both　of　Bi3+　and　Sm3+　doping　could　increase　the　red-emitting　intensity　and　corresponding　quantum　efficiency　(QE)　of　Na5Eu(WO4)4　host.　Furthermore,　the　color　rendering　index　of　the　commercial　yellow　phosphor　YAG:Ce3+　was　increased　from　44.5　to　50.8　and　50.2　by　mixed　with　Na5Eu　0.8Bi0.2(WO4)4　and　Na　5Eu0.96Sm0.04(WO4)4　phosphors　under　465　nm　excitation,　respectively.　The　CIE　chromaticity　coordinates　of　these　phosphors　are　close　to　the　standard　value　for　red.　Herein,　the　present　materials　are　promising　candidates　as　red　phosphors　for　white　light　emitting　diodes　with　near-UV/blue　GaN-based　chips.　©　2012　Elsevier　B.V.　All　rights　reserved.