A　series　of　new　Ln(14)-substituted　polyoxometalates,　H27Na16[(Ln(14)(H2O)W-4(OH)O-14)(WO4)(4)(GeW10O38)(6)]nH(2)O　(n　approximate　to　86)　(1-Ln,　Ln　=　Eu,　Gd,　Tb,　Dy,　Ho,　Er),　which　contain　14　Ln(3+)　and　6　{(1,5)-[GeW10O38](12-)}　units,　has　been　synthesized　in　one-pot　reactions.　As　the　first　14-Ln-containing　polyoxometalates,　the　octahedron-shaped　three-shell　structure　of　the　[(Ln(14)(H2O)W-4(OH)O-14)(WO4)(4)(GeW10O38)(6)](43-)　polyanion　is　made　up　of　a　W-4　tetrahedron,　a　Ln(14)W(4)　tetrahedron　and　a　Ge6W60　octahedron.　Compound　1-Dy　exhibits　frequency　dependent　magnetic　properties.　Compounds　1-Eu,　1-Tb　and　1-Dy　exhibit　the　characteristic　emission　bands　of　the　Ln(3+)　ion.