The heteropolytungstate [Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)~4](NH~4)~1~9.48H~2O is prepared by the reaction of Na~2WO~4.2H~2O with Sb~2O~3 and Ce(NO~3)~3.6H~2O. The structure of heteropolyanion Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4 is determined by X-ray diffraction analysis and elemental analysis. The cell parameters of [Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)~4](NH~4)~1~9.48H~2O: a=1.8908(6) nm, b=2.0032(14) nm, c=2.8653(12) nm, α=86.95(6)°, β=75.68(3)°, γ=67.52(5)°, V=9.706(9) nm^3, space group P1. The [Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)~4]^1^9^- anion possesses a large center group [Ce~3Sb~4W~2O~8(H~2O)~1~0]^1^7^+ attached by four β-B-(SbW~9O~3~3)^9^-, the center group contains three Ce(Ⅲ), two bridging {WO~2(H~2O)} groups and one {Sb~4O~4} group. The coordination number of all three Ce(Ⅲ) is nine however their coordination circumstances are different: Ce(1) and Ce(3) have the same coordination circumstance in which the cerium atoms are coordinated by four oxygen atoms of two (SbW~9O~3~3)^9^-, one oxygen atom of {Sb~4O~4}, one oxygen atom of one bridging {WO~2(H~2O)} and two oxygen atoms of two water molecules. Four antimony atoms form a tetrahedron in {Sb~4O~4} group. The anion belongs to C~s point group.

Key words: CERIUM COMPOUNDS, CRYSTAL STRUCTURE, ANTIMONY COMPOUNDS, TUNGSTATE, ANION, TUNGSTEN COMPOUNDS, HETEROPOLYACID