A novel coordination polymer, [Cu(en)_2]_2[Cu(en)_2αAsⅢ_8VⅣ_ 14O_ 42(HPO_4)]·8H_2O, was hydrothermally synthesized and structurally determined by Xray 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, D_c=2.551 Mg/m3, F(000)=5 364. The structural refinement indicated that the tilted compound was a chainlike coordination polymer based on cluster [αAs_8V_ 14O_ 42·(HPO_4)] 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 [αAs_8V_ 14O_ 42(HPO_4)] 6- to form the 1D chain. A novel coordination polymer, [Cu (en) _2] _2 [Cu (en) _2αAsⅢ_8VⅣ_14O_42 (HPO_4)] · 8H_2O, was hydrothermally synthesized and structurally determined by Xray single crystal diffraction. The crystal belongs to monoclinic system , space group P2 (1) / c, a = 1.501 0 (2) nm, b = 1.8609 (3) nm, c = 2.646 7 ) nm3, Z = 4, D_c = 2.551 Mg / m3, F (000) = 5 364. The structural refinement that that tilted compound was a chainlike coordination polymer based on cluster [αAs_8V_14O_42 · (HPO_4)] 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 [αAs_8V_14O_42 (HPO_4)] 6 to form the 1D chain.