A novel coordination polymer, [Cu（en）2]2[Cu（en）2αAsⅢ8VⅣ 14O 42（HPO4）]·8H2O, was hydrothermally synthesized and structurally determined by Xray single crystal diffraction. The crystal belongs to monoclinic system, space group P2（1）/c, a=1.501 0（2） nm, b=1.860 9（3） nm, c=2.646 7（4） nm, β=102.169（5）°, V=7.227（2） nm3, Z=4, Dc=2.551 Mg/m3, F（000）=5 364. The structural refinement indicated that the tilted compound was a chainlike coordination polymer based on cluster [αAs8V 14O 42·（HPO4）] 6- as the building blocks. Two of the three Cu（en）2 groups acted as the balance cation and the other one connected the anion cage [αAs8V 14O 42（HPO4）] 6- to form the 1D chain.
