The hydrothermal reactions of CuCl2· 2H2O, V2O5, and bidentate amines (2,2′-dipyridyl or ethylenediamine) gave the three new one-dimensional (1-D) vanadium oxide chain compounds, Cu(H2N(CH2)2NH2)[V2O6], 1, Cu(C10H8N2)[V2O6], 2, and Cu(C10H8N2)2[V2O6], 3, which contain copper coordination complexes covalently bound to vanadium oxide chains. All were structurally characterized via single-crystal X-ray diffraction. Crystal data are as follows: 1, monoclinic, space groupP21/n(No. 14) witha= 5.772(2) Å,b= 8.143(3) Å,c= 17.483(2) Å, β = 90.43(2)°,Z= 4, ρcalc= 2.599 g/cm3, andR(Rw) = 0.029 (0.028); 2, triclinic, space groupP1 (No. 2) witha= 10.114(2) Å,b= 10.839(3) Å,c= 5.810(3) Å, α = 94.75(3)°, β = 101.16(3)°, γ= 89.81(2)°,Z= 2, ρcalc= 2.27 g/cm3, andR(Rw)= 0.035 (0.044); 3, monoclinic, space groupP21/a(No. 14) witha= 10.478(2) Å,b= 13.779(2) Å,c= 14.513(3) Å, β = 100.39(1)°,Z= 4, and ρcalc= 1.849 g/cm−3withR(Rw) = 0.033 (0.034). While compounds 1 and 2 contain almost identical 1-D metal oxide chains composed of corner-sharing VO4tetrahedra with one oxygen atom from each tetrahedron bound to the copper complex, complex 3 consists of 1-D chains with a Cu(C10H8N2)2fragment bonded to every other VO4. Temperature-dependent magnetic measurements of 1 exhibit a maximum at 20 K, while 2, which possesses well-separated Cu2+centers, displays Curie–Weiss behavior from 5 to 300 K.