The hydrothermal syntheses, X-ray single-crystal structures, and some properties of Ba(VO)2(SeO3)2(HSeO3)2 and Ba8(VO)6 (Po4)2(HPO4)11 · 3H2O are described. Ba(VO)2(SeO3)2(HSeO3)2 contains a three-dimensional network of VO6 and (H)SeO3 polyhedra, linked via V-O-Se bonds. The Ba cation is 10-coordinate, the VO6 group contains a short vanadyl V[]O bond typical of VIV, and the (H)SeO3 groups are pyramidal. Magnetic susceptibility data are consistent with VIV and show paramagnetic behavior from 4 to 300 K. Crystal data for Ba(VO)2(SeO3)2(HSeO3)2:Mx = 781.06, monoclinic, space group P21/c (No. 14), a = 9.680(3) Å, b = 7.024(2) Å, c = 9.882(4) Å, β = 116.42(3)°, V = 601.75 Å3, Z = 2, R = 3.89%, Rw = 3.64% [1637 observed reflections with I > 3σ(I)]. Ba8(VO)6(PO4)2(HPO4)11 · 3H2O contains a complex network of VO6 and PO4/HPO4 groups, which form two different types of one-dimensional chains: one chain contains fairly regular VIVO6 and (H)PO4 groups; the other is built up from distorted VIVO6 octahedra and (hydrogen) phosphate groups. 10- and 13- coordinate Ba2+ cations complete the structure, which shows antiferromagnetic ordering of the VIV centers at ∼ 20 K. Crystal data for Ba8(VO)6(PO4)2(HPO4)11 · 3H2O:Mx Å 2800.05, monoclinic, space group C2/m (No. 12), a = 31.685(11) Å, b = 5.208(2) Å, c = 7.784(3) Å, β = 90.59(3)°, V = 1284.5(7) Å3, Z = 1, R = 4.03%, and Rw = 5.28% [1892 observed reflections with I > 3σ(1)].