The　title　complex　{[NaCu(BTC)(H2O)4]·2H　2O}n(H3-BTC　=　1,3,5-benzenetricarboxylic　acid)　has　been　synthesized　by　the　reaction　of　Cu(acac)2(acac　=　acetylacetone)　and　Na3BTC　in　the　mixed　solvent　of　methanol　and　water.　The　compound　was　characterized　by　single-crystal　X-ray　diffraction　analysis,　infrared　spectrum,　fluorescent　spectrum　and　TGA.　The　crystal　structure　is　of　monoclinic,　space　group　C2/c　with　a　=　2.1657(1)　nm,　b　=　1.12155(5)　nm,　c　=　1.35291　(7)　nm,　β　=　122.379(1)°,　V　=　2.7752(2)　nm3,　M　r　=　401.74,　Dc　=　1.923　Mg·m-3,　Z　=　8,　μ(Mo　Kα)　=　1.672　mm-1,　F(000)　=　1640,　GOF　=　1.014.　A　total　of　13298　reflections　were　collected　of　which　3339　were　unique.　The　structure　was　refined　to　R　=　0.0276　and　wR　=　0.0766　for　3176　observed　reflections　with　I　>　2σ　(I).　The　crystal　structure　forms　two-dimensional　double-sheet　network　by　the　extension　of　copper(II)/sodium(I)　trimesate　and　bridging　aqua　ligands.　There　is　an　obvious　interaction　between　metal　ions　Cu(II)　and　Na(I)　in　the　compound,　which　gives　an　infinite　one-dimensional　quasi-metal　string　complex.　Moreover,　the　complex　gives　a　strong　fluorescent　emission　band　at　420　nm　(λex　=　314　nm)　in　the　solid　state　at　room　temperature.